Preparation method of europium porcelain sand filter material with purification function

Abstract

The invention provides a preparation method of a europium porcelain sand filter material with a purification function, and belongs to the field of water pollution purification materials, and the method mainly comprises the following preparation steps: preparing europium modified porcelain sand, then preparing a titanium precursor, and finally carrying out hydrothermal membrane preparation. Through the step of modifying the porcelain sand with europium, part of metal elements on the surface of the porcelain sand are replaced by europium ions, and then through the step of hydrothermal film preparation, a titanium precursor reacts with the europium-modified porcelain sand to generate the europium titanate coating. The europium porcelain sand filter material disclosed by the invention has the characteristics of rich pores, strong filtering capacity, water flow impact resistance and the like; meanwhile, organic pollutants attached to the surface can be rapidly decomposed under illumination, and the performance of continuously treating the organic pollutants in wastewater is achieved.

Description

Technical Field

[0001] The invention belongs to the field of water pollution purification materials, and in particular relates to a method for preparing europium ceramic sand filter material with purification function. Background Art

[0002] Porcelain sand is made of high-quality kaolin, binder, pore former, anti-corrosion agent, etc., calcined at high temperature. It has a white appearance, hard texture, uniform particles, well-developed micropores, and high porosity. Porcelain sand filter material has the characteristics of large specific surface area, strong pollution interception ability, high water production, stable water quality, and long filtration cycle. It can meet the deep treatment of industrial wastewater and urban sewage with various complex components. The initial head loss of porcelain sand filter material is small, which is very beneficial for extending the working cycle of the filter tank; the final head loss of porcelain sand filter material is small, which can reduce the height of the filter tank and save infrastructure costs. Porcelain sand is uniform and regular, easy to load, not easy to lose, and has no secondary pollution. It is suitable for ion exchange, mechanical filter, valveless filter, reverse osmosis treatment device as pre-treatment filter material or resin support layer, and can be used as the cushion layer of activated carbon adsorber.

[0003] Since porcelain sand filter media can only serve as a pollutant interceptor and cannot decompose pollutants, organic pollutants will accumulate on the surface of the porcelain sand filter media, and gradually lose the function of intercepting pollutants as the treatment time increases. Therefore, after a period of use, the porcelain sand filter media must be regenerated, which increases time and cost in the continuous treatment process. Summary of the invention

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

[0005] The technical solution adopted by the present invention is:

[0006] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0007] Step 1: Europium modified porcelain sand

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

[0009] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

[0010] (3) filtering the mixture, and drying the obtained solid at 150° C. for 12 h to obtain europium-modified porcelain sand;

[0011] Step 2: Preparation of titanium precursor

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

[0013] (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;

[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 a titanium precursor;

[0015] Step 3: Hydrothermal film formation

[0016] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, transfer them into a hydrothermal reactor, control the reaction temperature at 210-220° C., the reactor pressure at 2.0-2.1 MPa, and the reaction time at 36 h;

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

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

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

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

[0021] Furthermore, the characteristics of the europium ceramic sand filter material are as follows: diameter 2-3 mm, volume density 2.32-2.39 g / cm 3 , porosity greater than 45%.

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

[0023] Compared with the prior art, the method for preparing the europium porcelain sand filter material with purification function of the present invention has the following advantages:

[0024] The invention adopts the step of modifying porcelain sand with europium, so that part of the metal elements on the surface of the porcelain sand are replaced by europium ions, and the europium ions are firmly combined with the surface of the porcelain sand; and then through the hydrothermal film-making step, the titanium precursor reacts with the europium-modified porcelain sand to generate a europium titanate coating, and the europium titanate coating is tightly 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 ability, and resistance to water flow impact; at the same time, it can quickly decompose organic pollutants attached to the surface under light, and has the performance of continuously treating organic pollutants in wastewater. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples where no specific conditions are indicated are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0026] Example 1

[0027] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0028] Step 1: Europium modified porcelain sand

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

[0030] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

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

[0032] Step 2: Preparation of titanium precursor

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

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

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

[0036] Step 3: Hydrothermal film formation

[0037] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, move them into a hydrothermal reactor, control the reaction temperature to 210° C., the reactor pressure to 2.0 MPa, and the reaction time to 36 h;

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

[0039] (3) Drying the filtered solid matter at 155° C. for 10 h, and then calcining at 650° C. for 150 min to obtain a europium ceramic sand filter material with a purification function; the europium ceramic sand filter material has a diameter of 2 to 3 mm and a volume density of 2.32 g / cm 3 , porosity 46%; the purification active ingredient of the europium porcelain sand filter material is the europium titanate coating coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating in the europium porcelain sand filter material is 3.3%.

[0040] Example 2

[0041] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0042] Step 1: Europium modified porcelain sand

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

[0044] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

[0045] (3) The mixture was filtered and the obtained solid was dried at 150° C. for 12 h to obtain europium-modified porcelain sand.

[0046] Step 2: Preparation of titanium precursor

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

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

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

[0050] Step 3: Hydrothermal film formation

[0051] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, move them into a hydrothermal reactor, control the reaction temperature to 210° C., the reactor pressure to 2.0 MPa, and the reaction time to 36 h;

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

[0053] (3) Dry the filtered solid matter at 155° C. for 10 h, and then calcine at 660° C. for 150 min to obtain a europium ceramic sand filter material with a purification function; the europium ceramic sand filter material has a diameter of 2 to 3 mm and a volume density of 2.33 g / cm 3 , porosity 46%; the purification active ingredient of the europium porcelain sand filter material is the europium titanate coating coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating in the europium porcelain sand filter material is 3.3%.

[0054] Example 3

[0055] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0056] Step 1: Europium modified porcelain sand

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

[0058] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

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

[0060] Step 2: Preparation of titanium precursor

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

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

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

[0064] Step 3: Hydrothermal film formation

[0065] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, transfer them into a hydrothermal reactor, control the reaction temperature to 215° C., the reactor pressure to 2.1 MPa, and the reaction time to 36 h;

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

[0067] (3) Dry the filtered solid matter at 155° C. for 10 h, and then calcine at 680° C. for 150 min to obtain a europium ceramic sand filter material with a purification function; the europium ceramic sand filter material has a diameter of 2 to 3 mm and a volume density of 2.35 g / cm 3 , porosity 46%; the purification active ingredient of the europium porcelain sand filter material is the europium titanate coating coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating in the europium porcelain sand filter material is 3.4%.

[0068] Example 4

[0069] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0070] Step 1: Europium modified porcelain sand

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

[0072] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

[0073] (3) The mixture was filtered and the obtained solid was dried at 150° C. for 12 h to obtain europium-modified porcelain sand.

[0074] Step 2: Preparation of titanium precursor

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

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

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

[0078] Step 3: Hydrothermal film formation

[0079] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, transfer them into a hydrothermal reactor, control the reaction temperature to 220° C., the reactor pressure to 2.1 MPa, and the reaction time to 36 h;

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

[0081] (3) Drying the filtered solid matter at 155° C. for 10 h, and then calcining at 700° C. for 150 min to obtain a europium ceramic sand filter material with a purification function; the europium ceramic sand filter material has a diameter of 2 to 3 mm and a volume density of 2.36 g / cm 3 , porosity 47%; the purification active ingredient of the europium porcelain sand filter material is the europium titanate coating coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating in the europium porcelain sand filter material is 3.5%.

[0082] Example 5

[0083] A method for preparing europium ceramic sand filter material with purification function comprises the following process steps:

[0084] Step 1: Europium modified porcelain sand

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

[0086] (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h;

[0087] (3) The mixture was filtered and the obtained solid was dried at 150° C. for 12 h to obtain europium-modified porcelain sand.

[0088] Step 2: Preparation of titanium precursor

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

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

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

[0092] Step 3: Hydrothermal film formation

[0093] (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, transfer them into a hydrothermal reactor, control the reaction temperature to 220° C., the reactor pressure to 2.1 MPa, and the reaction time to 36 h;

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

[0095] (3) Dry the filtered solid matter at 155° C. for 10 h, and then calcine at 710° C. for 150 min to obtain a europium ceramic sand filter material with a purification function; the europium ceramic sand filter material has a diameter of 2 to 3 mm and a volume density of 2.39 g / cm 3 , porosity 47%; the purification active ingredient of the europium porcelain sand filter material is the europium titanate coating coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating in the europium porcelain sand filter material is 3.5%.

Claims

1. A method for preparing europium ceramic sand filter material 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 of europium nitrate and 2.1-2.3 g of dodecyltrimethylammonium bromide to 300 mL of 0.3 mol / L hydrochloric acid solution and stir to form solution A; (2) Mix solution A and 30 g of porcelain sand and transfer into a flask, heat to 75°C, and reflux at this temperature for 2 h; (3) filtering the mixture, and drying the obtained solid at 150° C. for 12 h to obtain europium-modified porcelain sand; Step 2: Preparation of titanium precursor (1) Add 5-6 mL of n-butyl 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) Solution B and solution C were mixed and stirred in a constant temperature water bath at 35° C. for 15 min to obtain a titanium precursor; Step 3: Hydrothermal film formation (1) Mix the titanium precursor of step 2 and the europium-modified porcelain sand of step 1, transfer them into a hydrothermal reactor, control the reaction temperature at 210-220° C., the reactor pressure at 2.0-2.1 MPa, and the reaction time at 36 h; (2) After the reaction is completed, the mixture is filtered and washed with pure water; (3) The filtered solid matter was dried at 155° C. for 10 h, and then calcined at 650-710° C. for 150 min to obtain europium porcelain sand filter material with purification function.

2. The method for preparing a europium porcelain sand filter material with purification function according to claim 1, characterized in that: The porcelain sand in step (1) is a white spherical ball with a diameter of 2 to 3 mm and a bulk density of 2.31 to 2.38 g / cm 3 , compressive strength greater than 3.5×10 3 Pa, porosity 41%~43%.

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

4. The method for preparing a europium porcelain sand filter material with purification function according to claim 1, characterized in that: The characteristics of the europium ceramic sand filter material are as follows: diameter 2-3 mm, volume density 2.32-2.39 g / cm 3 , porosity greater than 45%.

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