Synthesis method of three-dimensional porous water treatment material and application of the three-dimensional porous water treatment material in purifying wastewater

Abstract

The application belongs to the field of wastewater treatment, and discloses a three-dimensional porous water treatment material synthesis method and application of purifying wastewater. The three-dimensional porous water treatment material is prepared by a hydrothermal synthesis method, and is hydrophobicity-regulated to form a multifunctional three-dimensional porous water treatment material. The surface of the three-dimensional porous water treatment material is rich in pore structures, and has the advantages of large adsorption capacity, improved adsorption performance on ciprofloxacin, and oil-water separation application. The three-dimensional porous water treatment material can remove antibiotics in wastewater and realize oil-water separation, and has the advantages of simple preparation process, excellent treatment effect, excellent adsorption performance, and wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of wastewater purification treatment technology in the environmental protection industry, and particularly relates to a preparation method of a multifunctional three-dimensional porous water treatment material and application thereof in purifying wastewater. BACKGROUND

[0002] Due to extensive and large-scale use, antibiotic drugs have been detected in various water environments worldwide, especially as the most commonly prescribed and used broad-spectrum fluoroquinolone antibiotic, ciprofloxacin is widely used for human treatment and veterinary applications; the pollution of ciprofloxacin in water is mainly derived from the discharge of incomplete metabolism in human body or pharmaceutical factory wastewater; the concentrations of ciprofloxacin in surface water, municipal wastewater, pharmaceutical factory wastewater and hospital wastewater are 0.1-100 ng / L, 100 ng / L-332.154 mg / L, 31 mg / L and 3-87 mg / L, respectively. The presence of ciprofloxacin and its metabolites in water bodies can have a negative impact on the growth, reproduction and survival of aquatic organisms. In addition, ciprofloxacin can also cause the development and spread of antibiotic resistance. Therefore, it is of great significance to realize efficient separation of ciprofloxacin in water for environmental safety.

[0003] Different water treatment technology methods and technologies have been developed to remove antibiotics in water, including adsorption method, biological treatment method, membrane separation method and catalytic oxidation method, etc. to remove ciprofloxacin in water environment. Among these methods, the adsorption method is considered as a very promising technology due to its simple operation, excellent performance and practicability in point source pollution emergency treatment. The characteristics of the material and the reaction conditions determine the removal effect and mechanism. Ciprofloxacin can form strong metal-ciprofloxacin complexes with multivalent metal ions and combine with functional groups. Therefore, metal-rich materials become ideal ciprofloxacin water treatment agents.

[0004] On the other hand, with the rapid development of China's leather, transportation, food, steel, petrochemical and other petroleum industries, the discharge and leakage of industrial oily wastewater have increased dramatically. As one of the volatile pollutants, oily wastewater not only pollutes groundwater and surface water, but also pollutes the atmosphere. Improper treatment of oily wastewater can cause serious ecological and environmental problems.

[0005] Foamed nickel is cheap, has a multi-layer and porous structure, low density, high mechanical properties and high thermal stability, etc. Therefore, it has been applied by some researchers to prepare water treatment agents for soluble pollutants and insoluble oil / water separation materials. When foamed nickel is used as a water treatment agent for soluble pollutants, it aims to utilize its unique structure to exhibit a large specific surface area; when used as an oil / water separation material, it aims to utilize its multi-level network structure. Therefore, it is of great significance to further develop water-soluble ciprofloxacin removal methods and insoluble oil / water separation methods based on foamed nickel. SUMMARY

[0006] In order to solve the above problems existing in the prior art, the present application aims at providing a three-dimensional porous water treatment material synthesis method and application of purifying wastewater, which can remove antibiotics in wastewater and realize oil-water separation, and has simple preparation process, excellent treatment effect and excellent adsorption performance.

[0007] The technical scheme adopted by the present application is:

[0008] A three-dimensional porous water treatment material synthesis method, comprising the following steps:

[0009] S01, preparing a cobalt hydroxide carbonate nanoneedle-foam nickel water treatment agent;

[0010] S011, preparing materials: acid washing and water washing the foam nickel to obtain clean foam nickel;

[0011] S012, preparing a uniform solution by mixing cobalt nitrate hexahydrate, ammonium fluoride and urea, and the mass ratio of the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 1:(0.12-0.15):(0.4-0.45);

[0012] S013, adding the foam nickel into the uniform solution, heating to 120-150 DEG C, and performing hydrothermal reaction for 12 hours;

[0013] S014, naturally cooling to room temperature, water washing and drying;

[0014] S015, repeating S011-S014 once again to obtain the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material;

[0015] S02, hydrophobic modification;

[0016] S021, adding the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material into an ethanol solution, and adding hexadecyl trimethoxysilane in the ethanol solution, and the mass ratio of the ethanol and the hexadecyl trimethoxysilane is 20:1;

[0017] S022, slowly adding glacial acetic acid to adjust the pH value of the solution;

[0018] S023, performing hydrolysis and condensation reaction of the hexadecyl trimethoxysilane for 12 hours;

[0019] S024, placing in an oven and drying at 60 DEG C to obtain the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material.

[0020] Further, the size of the foam nickel in the step S011 is 30mm*40mm*0.5mm;

[0021] The water washing processes in the steps S011 and S014 both use ultrapure water prepared by a pure water machine.

[0022] Further, in the step S012, the dosing amount of cobalt nitrate hexahydrate is 1.16g, the dosing amount of ammonium fluoride is 0.15g, and the dosing amount of urea is 0.5g; and the total volume of the uniform solution is 60mL.

[0023] Further, in the step S013, the uniform solution is heated to 130 DEG C, and the reaction time is 12 hours.

[0024] Further, in the step S014, the drying is performed at a temperature of 60 DEG C for 12 hours.

[0025] Further, in the step S021, the volume of the ethanol solution is 30mL, and 1.5mL of hexadecyl trimethoxysilane is added to the 30mL ethanol solution.

[0026] Further, in the step S022, glacial acetic acid is slowly added until the pH value of the ethanol solution is 4.3-4.8.

[0027] The application also relates to an application of a three-dimensional porous water treatment material in purifying wastewater, and a cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material prepared by using the above-mentioned synthesis method of a three-dimensional porous water treatment material.

[0028] P01, preparing a neutral solution containing antibiotics;

[0029] P02, controlling the environment: placing the neutral solution in a constant-temperature water bath, and covering and avoiding light;

[0030] P03, placing the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material into the neutral solution, and continuously oscillating and reacting.

[0031] Further, the following operation contents are further included:

[0032] In the step P01, multiple portions of the neutral solution are prepared, and the pH value of each portion of the neutral solution is adjusted;

[0033] In the step P02, the water bath temperature is 25 DEG C-30 DEG C;

[0034] In the step P03, the oscillation reaction is performed in a constant-temperature oscillator with a temperature of 25 DEG C-35 DEG C for 24h-30h.

[0035] Finally, in the step P03, the mass ratio of the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material to the antibiotics is: adsorbent: antibiotics = 1:(0.09-0.28).

[0036] The application has the following beneficial effects:

[0037] A three-dimensional porous water treatment material synthesis method and application of purifying wastewater, a cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material is prepared by a hydrothermal synthesis method, and hydrophobicity is controlled to form a multifunctional three-dimensional porous water treatment material, the surface pore structure is rich, has the advantage of large adsorption capacity, effectively improves the adsorption performance of ciprofloxacin, and can realize oil-water separation application. Both can remove antibiotics in wastewater and realize oil-water separation, the preparation process is simple, the treatment effect is excellent, the adsorption performance is excellent, and the application prospect is wide.

[0038] Compared with the prior art, the present application has at least the following beneficial effects:

[0039] 1. The cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material of the present application has large removal capacity and high removal efficiency for ciprofloxacin.

[0040] 2. Compared with other water treatment agents, the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material of the present application can obtain oil-water separation performance by only hydrophobic modification, and has multifunctional and multipurpose prospects.

[0041] 3. The cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material of the present application has a multi-layer and multi-porous three-dimensional structure, has high separation efficiency for a series of oil-water mixtures, and makes contributions to ecological environment protection. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 and Figure 2 The scanning electron microscope image of the hydrophobic cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material prepared by the three-dimensional porous water treatment material synthesis method of embodiment one of the present application. DETAILED DESCRIPTION

[0043] The technical solutions of the present application will be described clearly and completely below by combining specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. All other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0044] The application provides a three-dimensional porous water treatment material synthesis method and application of the three-dimensional porous water treatment material in purifying wastewater.

[0045] Specifically, the application provides a three-dimensional porous water treatment material synthesis method, which is specifically operated according to the following steps.

[0046] S01, preparing a cobalt carbonate hydroxide nanoneedle-foam nickel water treatment agent;

[0047] S011, preparing materials: acid washing and water washing the foam nickel to obtain clean foam nickel;

[0048] S012, preparing a uniform solution by mixing cobalt nitrate hexahydrate, ammonium fluoride and urea, wherein the mass ratio of the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 1:(0.12-0.15):(0.4-0.45);

[0049] S013, adding the foam nickel into the uniform solution, heating to 120-150 DEG C, and performing hydrothermal reaction for 12 hours;

[0050] S014, naturally cooling to room temperature, water washing and drying;

[0051] S015, repeating S011-S014 once again to obtain the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material;

[0052] S02, hydrophobic modification;

[0053] S021, adding the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material into an ethanol solution, adding hexadecyl trimethoxysilane in the ethanol solution, and the mass ratio of the ethanol to the hexadecyl trimethoxysilane being 20:1;

[0054] S022, slowly adding glacial acetic acid to adjust the pH value of the solution;

[0055] S023, performing hydrolysis and condensation reaction of the hexadecyl trimethoxysilane for 12 hours;

[0056] S024, placing in an oven and drying at 60 DEG C to obtain the hydrophobic cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material.

[0057] Further, the size of the foam nickel prepared in step S011 is 30mm*40mm*0.5mm.

[0058] The water washing process in steps S011 and S014 both use ultrapure water prepared by a pure water machine.

[0059] Further, the adding amount of cobalt nitrate hexahydrate in step S012 is 1.16g, the adding amount of ammonium fluoride is 0.15g, and the adding amount of urea is 0.5g; the total volume of the uniform solution is 60mL.

[0060] Further, in step S013, the uniform solution is heated to 130℃, and the reaction time is 12 hours.

[0061] Further, in step S014, drying is performed at a temperature of 60℃ for 12h.

[0062] Further, in step S021, the volume of the ethanol solution is 30mL, and 1.5mL of hexadecyl trimethoxysilane is added to the 30mL ethanol solution.

[0063] Further, in step S022, glacial acetic acid is slowly added until the pH value of the ethanol solution is 4.3-4.8.

[0064] The application also provides a use of a three-dimensional porous water treatment material for purifying wastewater, and the three-dimensional porous water treatment material is a cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material prepared by the above-mentioned synthesis method.

[0065] P01, preparing a neutral solution containing antibiotics;

[0066] Multiple portions of the neutral solution can be prepared, and the pH value of each portion of the neutral solution is adjusted;

[0067] P02, controlling the environment: placing the neutral solution in a constant temperature water bath, and the water bath temperature is 25-30℃; covering and avoiding light;

[0068] P03, placing the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material into the neutral solution, and continuously oscillating in a constant temperature oscillator with a temperature of 25-35℃ for 24-30h.

[0069] The mass ratio of the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material to the antibiotics is: cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material: antibiotics = 1:(0.09-0.28).

[0070] The application discloses a three-dimensional porous water treatment material synthesis method and application of the three-dimensional porous water treatment material to purifying wastewater.

[0071] 1. The cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material has large removal capacity and high removal efficiency for ciprofloxacin.

[0072] 2. Compared with other water treatment agents, the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material can obtain oil-water separation performance by only being hydrophobically modified, and has a multifunctional and multipurpose prospect.

[0073] 3. The cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material has a multilayer and porous three-dimensional structure, has high separation efficiency for a series of oil-water mixtures, and makes contributions to ecological environment protection.

[0074] Example 1

[0075] The adding dosage selection method of the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material for removing ciprofloxacin is implemented according to the following steps.

[0076] 1) Prepare a ciprofloxacin neutral solution with a concentration of 100 mg / L.

[0077] 2) Control the environment: the ciprofloxacin neutral solution is placed in a 25 DEG C constant-temperature water bath and is covered to avoid light.

[0078] 3) Put the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material with different areas (0.25, 0.5, 0.75, 1, 1.25 cm2) and a thickness of 0.5 mm into 20 mL of the ciprofloxacin neutral solution in 2), and oscillate for 24 h.

[0079] 4) The adding dosage of the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material used in this embodiment for treating ciprofloxacin wastewater is 1.25 cm2, and the ciprofloxacin removal rate is 96.2% under the optimal adding dosage.

[0080] Example 2

[0081] The optimal wastewater pH value selection method of the cobalt carbonate hydroxide nanoneedle-foam nickel water treatment material for removing ciprofloxacin is implemented according to the following steps.

[0082] 1) Preparation of ciprofloxacin solution: prepare a neutral ciprofloxacin solution with a concentration of 100 mg / L, and then adjust it to different pH values (2, 3, 4, 5, 6, 7, 8, 9, 10, 11) respectively.

[0083] 2) Control the environment: place the ciprofloxacin solution in a 25°C constant temperature water bath, cover and avoid light.

[0084] 3) Put the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material with a dosage of 1 cm2(thickness 0.5 mm) into 20 mL of ciprofloxacin solution in 2), and shake for 24 h.

[0085] 4) When the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material used in this example is used to treat ciprofloxacin wastewater, the removal rate of ciprofloxacin at the optimal wastewater pH value (pH = 8) is 95.2%.

[0086] Example 3

[0087] Example 3 implements the shortest equilibrium time selection method of cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material for removing ciprofloxacin, which is specifically operated according to the following steps:

[0088] 1) Preparation of ciprofloxacin solution: prepare a neutral ciprofloxacin solution with a concentration of 100 mg / L.

[0089] 2) Control the environment: place the ciprofloxacin neutral solution in a 25°C constant temperature water bath, cover and avoid light.

[0090] 3) Put the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material with different dosages of 12 cm2and thickness of 0.5 mm into 250 mL of ciprofloxacin neutral solution in 2), and shake for 24 h.

[0091] 4) When the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material used in this example is used to treat ciprofloxacin wastewater, the removal rate of ciprofloxacin at the shortest equilibrium time (8 hours) is 92.0%.

[0092] Example 4

[0093] Example 4 implements the selection method of the optimal oil-water mixture type of hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material for oil-water separation, which is specifically operated according to the following steps:

[0094] 1) Preparation of oil-water mixture: prepare 20 mL of water phase and 20 mL of oil phase (use chloroform, dichloromethane, toluene, xylene, petroleum ether respectively), and pour them into a beaker.

[0095] 2) Separation device customization: Customized a set of separation device, required the maximum liquid height to be less than 1.2 cm when pouring 20 mL of liquid into the upper part. A piece of hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material was clamped in the middle of the device.

[0096] 3) The five oil-water mixtures in 1) were slowly poured into the upper part of the device, and oil-water separation occurred. The water phase remained above the device, and the oil phase flowed into the lower part of the device.

[0097] 4) The hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material used in this example had a separation efficiency of 94.6% for the optimal oil-water mixture (chloroform / water) when used for oil-water separation.

[0098] Example 5

[0099] Example 5: Method for selecting the optimal storage water environment conditions for the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material for oil-water separation, which was performed according to the following steps:

[0100] 1) Prepare water environments: Prepare 20 mL of water and adjust the pH to 2, 4, 6, 7, 8, and 10, respectively.

[0101] 2) Soak the material: Place the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material in the six water environments in 1) for 24 hours, then rinse and dry at 60°C.

[0102] 3) Test the surface static contact angle of the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material in 2).

[0103] 4) The optimal water environment condition for the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material used in this example was pH = 7, with a surface static contact angle of 142.1°.

[0104] In summary, the present application is for the preparation and application of cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material and its hydrophobicity control material. The cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material can bind with ciprofloxacin, and there is also an electrostatic attraction between the material and ciprofloxacin under neutral solution pH conditions. Therefore, when this material is used to remove ciprofloxacin, it has superior removal performance, with a maximum ciprofloxacin removal rate of 96.2% in the example. Further hydrophobic regulation can obtain hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material with hydrophobic and oleophilic properties. Therefore, when it is applied to oil-water separation, it has good oil-water separation efficiency, with a maximum oil-water (chloroform / water) separation efficiency of 94.6% in the example.

[0105] The hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material can separate oil / water mixtures, which can be chloroform / water, dichloromethane / water, toluene / water, xylene / water and petroleum ether / water layered liquids. The separation process is driven by gravity of the liquid, and the maximum intrusion pressure is 117.6 Pa, that is, the maximum water phase height that can be tolerated is 1.2 cm. The verification process can further increase the water phase height to be greater than 1.2 cm, and then the water phase penetrates the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material, which can be verified.

[0106] The present application is not limited to the above-mentioned optional embodiments, and anyone can derive other various forms of products under the inspiration of the present application, but regardless of any changes in shape or structure, any technical solutions falling within the scope defined by the claims of the present application fall within the protection scope of the present application.

Claims

1. Use of a three-dimensional porous water treatment material for purifying wastewater, characterized in that: The three-dimensional porous water treatment material synthesis method comprises the following steps: S01, preparing a cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material; S011, preparing materials: acid washing and water washing the foam nickel to obtain clean foam nickel; S012, preparing a uniform solution by mixing cobalt nitrate hexahydrate, ammonium fluoride and urea, and the mass ratio of the three is 1:(0.12-0.15):(0.4-0.45); S013, adding the foam nickel into the uniform solution and heating to 120-150 DEG C, and then performing hydrothermal reaction for 12 hours; S014, naturally cooling to room temperature, and then water washing and drying; S015, repeating steps S011-S014 once again to obtain the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material; S02, hydrophobic modification; S021, adding the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material into an ethanol solution, and adding hexadecyl trimethoxysilane into the ethanol solution, and the mass ratio of ethanol to hexadecyl trimethoxysilane is 20:1; S022, slowly adding glacial acetic acid to adjust the pH value of the solution; S023, performing hydrolysis and condensation reaction of the hexadecyl trimethoxysilane for 12 hours; S024, drying in an oven at 60 DEG C to obtain the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material; The application uses the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material prepared by the three-dimensional porous water treatment material synthesis method; Specifically comprising the following operation steps: P01, preparing a neutral solution containing antibiotics; P02, controlling the environment: placing the neutral solution in a constant temperature water bath and covering to avoid light; P03, putting the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material into the neutral solution and continuously oscillating to react; The application also comprises using the hydrophobic cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material prepared by the three-dimensional porous water treatment material synthesis method to separate oil and water; The separated oil / water mixture is a layered liquid of chloroform / water, dichloromethane / water, toluene / water, dimethylbenzene / water and petroleum ether / water.

2. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: The size of the foam nickel prepared in step S011 is 30 mm*40 mm*0.5 mm; The water washing process in steps S011 and S014 both uses ultrapure water prepared by a pure water machine.

3. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: In step S012, the addition amount of cobalt nitrate hexahydrate is 1.16 g, the addition amount of ammonium fluoride is 0.15 g, and the addition amount of urea is 0.5 g; the total volume of the uniform solution is 60 mL.

4. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: In step S013, the uniform solution is heated to 130 DEG C, and the reaction time is 12 hours.

5. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: In step S014, drying is performed at a temperature of 60 DEG C for 12 hours.

6. Use of the three-dimensional porous water treatment material according to claim 3 for purifying wastewater, characterized in that: In step S021, the volume of the ethanol solution is 30 mL, and 1.5 mL of hexadecyl trimethoxysilane is added into the 30 mL ethanol solution.

7. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: In step S022, glacial acetic acid is slowly added until the pH value of the ethanol solution is 4.3-4.

8.

8. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: The application also comprises the following operation content: In step P01, multiple portions of neutral solution are prepared, and the pH value of each portion of the neutral solution is adjusted respectively; The water bath temperature in the step P02 is 25-30 DEG C. In the step P03, the reaction is oscillated in a constant temperature oscillator with a temperature of 25-35 DEG C for 24-30 hours.

9. Use of the three-dimensional porous water treatment material according to claim 1 for purifying wastewater, characterized in that: In the step P03, the mass ratio of the cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material to the antibiotic is: cobalt hydroxide carbonate nanoneedle-foam nickel water treatment material: antibiotic = 1: (0.09-0.28).

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