A porous water treatment material and a method for making the same

Abstract

The present application relates to a kind of porous water treatment materials and its preparation method, belong to environmental pollution purification material field.The method described in the present application main preparation steps include: diatomite pore, preparation vanadium-iron-indium solution and film deposition.The present application with the diatomite pore of fixed hole as carrier material, vanadium acid iron-oxidized indium composite film is generated in diatomite surface and pore interior.The porous water treatment material has larger adsorption capacity, can adsorb organic pollutants in water;Vanadium acid iron-oxidized indium composite film has the activity of degrading organic pollutants under illumination.The porous water treatment material can be quickly separated from water and recycled after water treatment, has wide application prospect in various organic wastewater treatment fields.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of environmental pollution purification materials, and particularly relates to a porous water treatment material and a preparation method thereof. BACKGROUND

[0002] Industrial and domestic wastewater contains various pollutants, and organic pollutants have great harm to the environment and human health. Therefore, the wastewater must be deeply purified to achieve the purpose of not polluting the environment.

[0003] There are many methods for treating organic contaminated wastewater, such as common biochemical treatment technology. However, the key microorganisms in the biochemical technology are easily affected by toxic and harmful organic pollutants, and cannot make the wastewater treatment reach a satisfactory standard. Adsorption materials can effectively remove pollutants in water, but the biggest problem of such materials is that they have a certain adsorption saturation capacity, and cannot continue to adsorb pollutants when the materials are saturated. Physical treatment methods mainly include adsorption and membrane separation, but the physical method only transfers the pollutants in the organic wastewater and does not fundamentally degrade to achieve the purpose of eliminating pollutants, and has low treatment efficiency, large material consumption and high cost, and is difficult to popularize and use. In addition, chemical treatment methods mainly include chemical flocculation and chemical oxidation. The chemical flocculation method adds a certain amount of flocculant to the organic wastewater to produce flocculation with the organic substances in the organic wastewater to generate sediment or suspension, so as to achieve the purpose of separation. This method is relatively economical and effective in organic wastewater treatment, but the generated sediment sludge needs further treatment. SUMMARY

[0004] In view of the problems in the prior art, the present application aims to provide a preparation method of a porous water treatment material, which can be used in the photocatalytic purification process of organic pollutants in wastewater.

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

[0006] A porous water treatment material prepared by the above method, wherein the bulk density of the porous water treatment material is 0.65-0.68 g / cm 3 , the specific surface area is 66-69 m 2 / g, and the pore volume is 0.73-0.77 cm 3 / g.

[0007] Further, the porous water treatment material maintains stable structure and performance below 450℃.

[0008] A preparation method of the porous water treatment material, comprising the following process steps:

[0009] Step 1: diatomite pore setting

[0010] (1) In a flask, 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomite are added, and stirred in a 85°C constant temperature water bath for 120 min. After cooling, filtration is performed, and the solid is washed with pure water and then filtered to obtain solid A;

[0011] (2) Solid A is subjected to the above step twice to obtain solid B. Solid B is dried at 180°C for 15 h, and then calcined at 550-560°C for 3 h, and cooled to room temperature to obtain diatomite with regular pores;

[0012] Step 2: Preparation of vanadium-iron-indium solution

[0013] In 130 mL of pure water, 13-17 g of ferrous sulfate, 11-13 g of sodium metavanadate, and 8-9.5 g of indium nitrate are added to form solution A. In 60 mL of ethanol, 5-6 g of emulsifier Tween 60 and 3-3.6 g of polyethylene glycol with a molecular weight of 6000 are added to form solution B. Solution B is slowly added to solution A, and incubated in a 35°C constant temperature water bath for 30 min to obtain a vanadium-iron-indium solution;

[0014] Step 3: Membrane deposition

[0015] The diatomite with regular pores prepared in step 1 is mixed with the vanadium-iron-indium solution, and transferred to a stainless steel hydrothermal reactor, and reacted at 220-250°C for 72 h. After cooling, filtration is performed, and the solid is washed with pure water and then filtered to obtain solid C. Solid C is dried at 190°C for 22 h, and then calcined at 460-510°C for 5 h, and cooled to room temperature to obtain a porous water treatment material.

[0016] Further, the diatomite in step (1) has a particle size of 18-22 mm, a bulk density of 0.6 g / cm 3 , a specific surface area of 75 m 2 / g, and a pore volume of 0.82 cm 3 / g.

[0017] Further, the diatomite with regular pores prepared in step (1) has a surface and pores inside which generate a composite film of iron vanadate-indium oxide, and the composite film is firmly combined with the diatomite.

[0018] Further, the composite film of iron vanadate-indium oxide is composed of two photocatalytically active substances, iron vanadate and indium oxide, wherein the mass percentage of iron vanadate in the porous water treatment material is 3.8%-4.3%, and the mass percentage of indium oxide in the porous water treatment material is 2.7%-3.1%. The relative mass ratio of iron vanadate and indium oxide is the key to ensuring the stability and photocatalytic performance of the material.

[0019] This invention discloses a porous water treatment material and its preparation method. Compared with existing technologies, the advantages are as follows: This invention uses porous diatomaceous earth as a carrier material to generate an iron vanadate-indium oxide composite membrane on the surface and inside the pores of the diatomaceous earth. This porous water treatment material has a large adsorption capacity and can adsorb organic pollutants in water. Under light irradiation, the iron vanadate-indium oxide composite membrane coated on the porous water treatment material exhibits activity in degrading organic pollutants, enabling the material to continuously remove organic pollutants from water. This porous water treatment material has a lower density than water, allowing for rapid separation and recycling after water treatment, and has broad application prospects in various organic wastewater treatment fields. Detailed Implementation

[0020] 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.

[0021] Unless otherwise specified, all chemical raw materials are pure materials.

[0022] Example 1

[0023] A method for preparing a porous water treatment material includes the following process steps:

[0024] Step 1: Diatomaceous earth hole setting

[0025] (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A.

[0026] (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 550℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores.

[0027] Step 2: Preparation of vanadium-iron-indium solution

[0028] Add 13g of ferrous sulfate, 11g of sodium metavanadate, and 8g of indium nitrate to 130mL of pure water and stir to form solution A; add 5g of emulsifier Tween 60 and 3g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B; slowly add solution B to solution A and keep warm in a constant temperature water bath at 35℃ for 30min to obtain vanadium-iron-indium solution.

[0029] Step 3: Film Deposition

[0030] The diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred to a stainless steel hydrothermal reactor. The mixture was reacted at 220°C for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190°C for 22 hours, then calcined at 460°C for 5 hours and cooled to room temperature to obtain a porous water treatment material with a bulk density of 0.65 g / cm³. 3 Specific surface area 69m² 2 / g, pore volume 0.77cm³ 3 / g.

[0031] In step (1), a ferric vanadate-indium oxide composite membrane is formed on the surface and inside the pores of the diatomaceous earth with fixed pores. The ferric vanadate-indium oxide composite membrane is composed of two photocatalytic active substances, ferric vanadate and indium oxide, wherein ferric vanadate accounts for 3.8% of the mass of the porous water treatment material and indium oxide accounts for 2.7% of the mass of the porous water treatment material.

[0032] Example 2

[0033] A method for preparing a porous water treatment material includes the following process steps:

[0034] Step 1: Diatomaceous earth hole setting

[0035] (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A.

[0036] (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 550℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores.

[0037] Step 2: Preparation of vanadium-iron-indium solution

[0038] Add 14g of ferrous sulfate, 11.5g of sodium metavanadate, and 8.3g of indium nitrate to 130mL of pure water and stir to form solution A; add 5.2g of emulsifier Tween 60 and 3.1g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B; slowly add solution B to solution A and keep it in a constant temperature water bath at 35℃ for 30min to obtain vanadium-iron-indium solution.

[0039] Step 3: Film Deposition

[0040] The diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred to a stainless steel hydrothermal reactor. The mixture was reacted at 225°C for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190°C for 22 hours, then calcined at 470°C for 5 hours and cooled to room temperature to obtain a porous water treatment material with a bulk density of 0.66 g / cm³. 3 Specific surface area 68m² 2 / g, pore volume 0.76cm³ 3 / g.

[0041] In step (1), a ferric vanadate-indium oxide composite membrane is formed on the surface and inside the pores of the diatomaceous earth with fixed pores. The ferric vanadate-indium oxide composite membrane is composed of two photocatalytic active substances, ferric vanadate and indium oxide, wherein ferric vanadate accounts for 3.9% of the mass of the porous water treatment material and indium oxide accounts for 2.8% of the mass of the porous water treatment material.

[0042] Example 3

[0043] A method for preparing a porous water treatment material includes the following process steps:

[0044] Step 1: Diatomaceous earth hole setting

[0045] (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A.

[0046] (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 555℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores.

[0047] Step 2: Preparation of vanadium-iron-indium solution

[0048] Add 15g of ferrous sulfate, 12g of sodium metavanadate, and 8.8g of indium nitrate to 130mL of pure water and stir to form solution A; add 5.5g of emulsifier Tween 60 and 3.3g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B; slowly add solution B to solution A and keep it in a constant temperature water bath at 35℃ for 30min to obtain vanadium-iron-indium solution.

[0049] Step 3: Film Deposition

[0050] The diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred to a stainless steel hydrothermal reactor. The mixture was reacted at 235°C for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190°C for 22 hours, then calcined at 480°C for 5 hours and cooled to room temperature to obtain a porous water treatment material with a bulk density of 0.66 g / cm³. 3 Specific surface area 67m² 2 / g, pore volume 0.75cm³ 3 / g.

[0051] In step (1), a ferric vanadate-indium oxide composite membrane is formed on the surface and inside the pores of the diatomaceous earth with fixed pores. The ferric vanadate-indium oxide composite membrane is composed of two photocatalytic active substances, ferric vanadate and indium oxide, wherein ferric vanadate accounts for 4.0% of the mass of the porous water treatment material and indium oxide accounts for 2.9% of the mass of the porous water treatment material.

[0052] Example 4

[0053] A method for preparing a porous water treatment material includes the following process steps:

[0054] Step 1: Diatomaceous earth hole setting

[0055] (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A.

[0056] (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 560℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores.

[0057] Step 2: Preparation of vanadium-iron-indium solution

[0058] Add 16g of ferrous sulfate, 12.3g of sodium metavanadate, and 9.2g of indium nitrate to 130mL of pure water and stir to form solution A; add 5.8g of emulsifier Tween 60 and 3.5g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B; slowly add solution B to solution A and keep it in a constant temperature water bath at 35℃ for 30min to obtain vanadium-iron-indium solution.

[0059] Step 3: Film Deposition

[0060] The diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred to a stainless steel hydrothermal reactor. The mixture was reacted at 240°C for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190°C for 22 hours, then calcined at 495°C for 5 hours and cooled to room temperature to obtain a porous water treatment material with a bulk density of 0.67 g / cm³. 3 Specific surface area 67m² 2 / g, pore volume 0.75cm³ 3 / g.

[0061] In step (1), a ferric vanadate-indium oxide composite membrane is formed on the surface and inside the pores of the diatomaceous earth with fixed pores. The ferric vanadate-indium oxide composite membrane is composed of two photocatalytic active substances, ferric vanadate and indium oxide, wherein ferric vanadate accounts for 4.2% of the mass of the porous water treatment material and indium oxide accounts for 3.0% of the mass of the porous water treatment material.

[0062] Example 5

[0063] A method for preparing a porous water treatment material includes the following process steps:

[0064] Step 1: Diatomaceous earth hole setting

[0065] (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A.

[0066] (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 560℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores.

[0067] Step 2: Preparation of vanadium-iron-indium solution

[0068] Add 17g of ferrous sulfate, 13g of sodium metavanadate, and 9.5g of indium nitrate to 130mL of pure water and stir to form solution A; add 6g of emulsifier Tween 60 and 3.6g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B; slowly add solution B to solution A and keep it in a constant temperature water bath at 35℃ for 30min to obtain vanadium-iron-indium solution.

[0069] Step 3: Film Deposition

[0070] The diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred to a stainless steel hydrothermal reactor. The mixture was reacted at 250°C for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190°C for 22 hours, then calcined at 510°C for 5 hours and cooled to room temperature to obtain a porous water treatment material with a bulk density of 0.68 g / cm³. 3 Specific surface area 66m² 2 / g, pore volume 0.73cm³ 3 / g.

[0071] In step (1), a ferric vanadate-indium oxide composite membrane is formed on the surface and inside the pores of the diatomaceous earth with fixed pores. The ferric vanadate-indium oxide composite membrane is composed of two photocatalytic active substances, ferric vanadate and indium oxide, wherein ferric vanadate accounts for 4.3% of the mass of the porous water treatment material and indium oxide accounts for 3.1% of the mass of the porous water treatment material.

Claims

1. A method for preparing a porous water treatment material, characterized in that, The process includes the following steps: Step 1: Diatomaceous earth hole setting (1) Add 680 mL of 0.25 mol / L hydrochloric acid solution and 50 g of diatomaceous earth to a flask, place it in an 85°C constant temperature water bath and stir for 120 min. After cooling, filter, wash with pure water and filter again to obtain solid A. (2) Repeat the previous step twice to obtain solid B; dry solid B at 180℃ for 15h, then calcine at 550~560℃ for 3h, and cool to room temperature to obtain diatomaceous earth with fixed pores. Step 2: Preparation of vanadium-iron-indium solution Add 13-17g of ferrous sulfate, 11-13g of sodium metavanadate, and 8-9.5g of indium nitrate to 130mL of pure water and stir to form solution A; add 5-6g of emulsifier Tween 60 and 3-3.6g of polyethylene glycol with a molecular weight of 6000 to 60mL of ethanol and stir to form solution B. Solution B was slowly added to solution A and kept in a constant temperature water bath at 35℃ for 30 minutes to obtain a vanadium-iron-indium solution. Step 3: Film Deposition The porous diatomaceous earth obtained in step 1 was mixed with a vanadium-iron-indium solution and transferred into a stainless steel hydrothermal reactor. The mixture was reacted at 220~250℃ for 72 hours, cooled, filtered, washed with pure water, and filtered again to obtain solid C. Solid C was dried at 190℃ for 22 hours, then calcined at 460~510℃ for 5 hours and cooled to room temperature to obtain a porous water treatment material. The diatomaceous earth with fixed pores obtained in step (1) forms an iron vanadate-indium oxide composite film on the surface and inside the pores. The iron vanadate-indium oxide composite membrane is composed of two photocatalytically active substances, iron vanadate and indium oxide, wherein the iron vanadate accounts for 3.8%~4.3% of the porous water treatment material by mass, and the indium oxide accounts for 2.7%~3.1% of the porous water treatment material by mass. The porous water treatment material has a bulk density of 0.65~0.68 g / cm³. 3 Specific surface area 66~69m² 2 / g, pore volume 0.73~0.77cm³ 3 / g; The porous water treatment material maintains structural and performance stability below 450℃.

2. The method for preparing a porous water treatment material according to claim 1, characterized in that, The diatomaceous earth in step (1) has a particle size of 18-22 mm and a bulk density of 0.6 g / cm³. 3 Specific surface area 75m² 2 / g, pore volume 0.82cm³ 3 / g.