CN106139647B - Metal ion-purposes of the Polybenzoxazine micro-nano ball as water-oil separating material - Google Patents

Abstract

The invention discloses the use of metal ion-polybenzoxazine micro-nanospheres as an oil-water separation material. Metal ion-polybenzoxazine micro-nanospheres have ultra-low density and good oil-water separation ability, as well as high mechanical and chemical stability, not only can be used under high temperature and high pressure, but also can effectively resist acid, alkali, Salt corrosion can not only effectively separate water/oil emulsions that cannot be separated by general mesh materials, but also has the advantages of high separation efficiency, high mechanical strength, and recyclability, and has broad practical application prospects.

Description

Application of metal ion-polybenzoxazine micro-nanospheres as oil-water separation material

technical field

The invention relates to a new application of metal ion-polybenzoxazine micronanospheres as an oil-water separation material.

Background technique

The rapidly growing global energy demand has increased the exploitation of offshore oil, followed by frequent oil spill accidents at sea, resulting in a large amount of crude oil polluting sea areas and causing extremely serious harm to the ecological environment; at the same time, daily life and industrial production It also produces a large amount of oily wastewater, which has a negative impact on the human living environment. How to effectively collect and remove oil from water has become a world-class challenge and has attracted extensive attention.

Traditional oil removal methods include fence oil absorption method, in-situ combustion method, chemical dispersion method, solidification method and so on. However, these methods are relatively expensive, relatively inefficient, and even cause secondary pollution. Compared with traditional methods, the use of adsorption materials for oil-water separation is considered to be a simple and feasible method. So far, adsorption materials such as zeolite, activated carbon, and plant/carbon fiber have been used as oil adsorption materials, but these materials also absorb water while absorbing oil, which greatly reduces the oil-water separation efficiency. The discovery of superhydrophobic/superoleophilic materials with special wettability on the surface can selectively absorb oil substances, so precious petroleum resources can be selectively removed and recovered from water.

Contents of the invention

The purpose of the present invention is to provide a new application of metal ion-polybenzoxazine micro-nanospheres as an oil-water separation material.

The metal ion-polybenzoxazine micro-nanospheres are polymerized by benzoxazine and metal ions to generate metal ion-polybenzoxazine micelles, and then the micelles are solidified by the inverse suspension method be made of.

Preferably, the preparation method of the metal ion-polybenzoxazine micro-nanospheres comprises the following steps:

1) Mix benzoxazine and metal ion at a molar ratio of 5: (0.2-1), dissolve in an organic solvent, and stir ultrasonically at room temperature to obtain metal ion-polybenzoxazine micelles;

3) Using glycerin or silicone oil as a medium, the metal ion-polybenzoxazine micelles are solidified at 120-240° C., and the metal ion-polybenzoxazine micro-nanospheres are obtained after the medium is eluted.

Further preferably, the molar ratio of the benzoxazine to the metal ion is 5:0.5.

Further preferably, the metal ion is Fe ³⁺ or Zn ²⁺ or Cu ²⁺ .

In the present invention, after benzoxazine is doped with metal ions and solidified by reverse-phase suspension method, superhydrophobic/superlipophilic metal ion-polybenzoxazine micro-nanospheres with a large number of pores are successfully synthesized, with higher pores The high oil absorption rate makes it have a higher oil absorption rate. The metal ion-polybenzoxazine micro-nanospheres synthesized by this method not only maintain the advantages of polybenzoxazine resin such as environmental protection, heat resistance, flame retardancy, and good stability, but also It improves the hydrophobicity of polybenzoxazine resin, has ultra-low density and good oil-water separation ability, has high water contact angle and low rolling angle, and has surface self-cleaning function.

In the present invention, another important feature is that it has high mechanical stability and chemical stability, not only can be used under high temperature and high pressure, but also can effectively resist the corrosion of acid, alkali and salt, super hydrophobic/super lipophilic metal ion - Polybenzoxazine micro-nanospheres can not only effectively separate water/oil emulsions that cannot be separated by general mesh materials, but also have the advantages of high separation efficiency, high mechanical strength, and recyclability, and have broad practical application prospects.

Description of drawings

Figure 1: The contact angles of water, oil, acid, alkali, and salt solutions on the surface of metal ion-polybenzoxazine micro-nanospheres;

Figure 2: Rolling angle of water on the surface of metal ion-polybenzoxazine micro-nanospheres;

Figure 3: The contact angle of water on the surface of metal ion-polybenzoxazine micro-nanospheres under high temperature and pressure;

Figure 4: Oil absorption speed of metal ion-polybenzoxazine micro-nanospheres;

Figure 5: Oil-absorbing reuse of metal ion-polybenzoxazine micro-nanospheres;

Figure 6: Efficiency of metal ion-polybenzoxazine micro-nanospheres for separation of water/oil emulsions.

Detailed ways

The present invention will be described in detail below in conjunction with examples.

Example 1

The synthetic method of metal ion-polybenzoxazine micro-nanosphere comprises the following steps:

1) In a 250ml three-neck flask equipped with a stirring and condensing device, add 0.1mol bisphenol A, 0.1mol melamine and 0.1mol formaldehyde solution, add 100ml methanol as a reaction solvent, react at 70°C for 3 hours, and then spin evaporate to remove the solvent , to benzoxazine.

2) Add 0.5 mol benzoxazine and 0.1 mol FeCl ₃ , 20 ml methanol and 80 ml toluene into a 250 ml beaker as solvents, and ultrasonically mix at room temperature to obtain metal ion (Fe)-polybenzoxazine micelles.

3) Add 150ml of silicone oil into a 250ml beaker, heat to 240°C, add metal ion (Fe)-polybenzoxazine micelles to the silicone oil to solidify, filter with 400 mesh gauze after the reaction, and elute the adsorption with petroleum ether Silicone oil on the surface of the micro-nanospheres, to obtain metal ions-polybenzoxazine micro-nanospheres.

Example 2

The synthetic method of metal ion-polybenzoxazine micro-nanosphere comprises the following steps:

1) In a 250ml three-necked flask equipped with a stirring and condensing device, add 0.2mol of bisphenol fluorene, 0.1mol of melamine and 0.2mol of formaldehyde solution, add 100ml of methanol as a reaction solvent, react at 60°C for 3 hours, and then spin evaporate to remove the solvent , to benzoxazine.

2) Add 0.5 mol benzoxazine and 0.05 mol ZnCl ₂ into a 250 ml beaker, add 40 ml methanol and 80 ml toluene as solvents, and ultrasonically mix at room temperature to obtain metal ion (Zn)-polybenzoxazine micelles.

3) Add 150ml of silicone oil to a 250ml beaker, heat to 200°C, add metal ion (Zn)-polybenzoxazine micelles to the silicone oil to solidify, filter with 400-mesh gauze after the reaction, and elute the adsorption with petroleum ether Silicone oil on the surface of the micro-nanospheres, to obtain metal ions-polybenzoxazine micro-nanospheres.

Example 3

The synthetic method of metal ion-polybenzoxazine micro-nanosphere comprises the following steps:

1) In a 250ml three-neck flask equipped with a stirring and condensing device, add 0.1mol phenol, 0.3mol melamine and 0.3mol formaldehyde solution, add 100ml methanol as a reaction solvent, react at 90°C for 3h, and remove the solvent by rotary evaporation after completion, to obtain benzoxazines.

2) Add 0.5 mol benzoxazine and 0.02 mol CuCl ₂ into a 250 ml beaker, add 60 ml methanol and 60 ml toluene as solvents, and ultrasonically mix at room temperature to obtain metal ion (Cu)-polybenzoxazine micelles.

3) Add 150ml of silicone oil to a 250ml beaker, heat to 120°C, add metal ion (Cu)-polybenzoxazine micelles to the silicone oil to solidify, filter with 400 mesh gauze after the reaction, and elute the adsorption with petroleum ether Silicone oil on the surface of the micro-nanospheres, to obtain metal ions-polybenzoxazine micro-nanospheres.

Example 4

1. Hydrophobicity/lipophilicity and acid, alkali and salt tolerance experiments of metal ion-polybenzoxazine micro-nanospheres:

1) OCA-15EC contact angle measuring instrument, respectively test the contact angle of water and oil on the surface of metal ion-polybenzoxazine micro-nanospheres, taking ultrapure water as an example for water and diesel as an example for oil.

2) Tilt the sample stage to test the rolling angle of the water droplet on the surface of the metal ion-polybenzoxazine micro-nanosphere.

3) Prepare HCl aqueous solution, NaCl aqueous solution, and NaOH aqueous solution with a Ph of 1, 7, and 14 and a concentration of 1 M, respectively.

4) Test the contact angles of the above three aqueous solutions on the surface of metal ion-polybenzoxazine micro-nanospheres. The results are shown in Figure 1 and Figure 2.

It can be seen from the experimental results that the contact angle of the material of the present invention to diesel oil is close to zero, while the contact angles to the three aqueous solutions are all about 150 degrees. Proved to have very good hydrophobic, lipophilic effect. The contact angle to ultrapure water is greater than 150 degrees, and the rolling angle is less than 1 degree, which has obvious self-cleaning function characteristics.

2. High temperature and high pressure tolerance experiments of metal ion-polybenzoxazine micro-nanospheres:

1) Put the metal ion-polybenzoxazine micro-nanospheres in an oven at 150°C, and take them out after 10 hours to test the contact angle of water on the surface.

2) Put the metal ion-polybenzoxazine micro-nanosphere under a pressure of 15 MPa, take it out after 1 hour, and test the contact angle of water on its surface.

The results are shown in Figure 3. From the experimental results, it can be seen that the hydrophobicity of the material of the present invention is not affected by temperature and pressure, and can be used under severe conditions.

3. Oil absorption speed experiment of metal ion-polybenzoxazine micro-nanospheres:

1) Dry metal ion-polybenzoxazine micro-nanospheres and 400-mesh nylon cloth in an oven at 60°C to constant weight.

2) Accurately weigh a certain mass of dry metal ion-polybenzoxazine micro-nanospheres, wrap them with nylon cloth to make a metal ion-polybenzoxazine micro-nanosphere oil-absorbing package, and accurately weigh its mass .

3) Completely immerse the oil-absorbing bag in the beaker containing 0# diesel oil, take it out at 10s, 60s, 300s, 600s, 1800s, and 3600s and let it stand for 5s before weighing.

4) The oil absorption is the oil absorption after subtracting the mass of the oil absorption pack from the mass after oil absorption, and the ratio of the oil absorption to the mass of the metal ion-polybenzoxazine micro-nanosphere is the oil absorption.

The results are shown in Figure 4. From the experimental results, it can be seen that the material of the present invention can quickly absorb oil, and the speed is stable, with little change over time.

4. Metal ion-polybenzoxazine micro-nanosphere oil absorption reuse and recovery experiments:

1) Dry metal ion-polybenzoxazine micro-nanospheres and 400-mesh nylon cloth in an oven at 60°C to constant weight.

2) Accurately weigh a certain mass of dry metal ion-polybenzoxazine micro-nanospheres, wrap them with nylon cloth to make a metal ion-polybenzoxazine micro-nanosphere oil-absorbing package, and accurately weigh its mass .

3) Submerge the oil-absorbing bag completely in the beaker containing 0# diesel oil, take it out after 10s and let it stand for 5s, then weigh it.

4) The oil absorption is the mass after oil absorption minus the mass of the oil absorption pack, and the oil absorption metal ion-polybenzoxazine micro-nanosphere mass ratio is the oil absorption rate.

5) After weighing, squeeze the oil-absorbing bag to collect most of the diesel oil, then use petroleum ether as a solvent to Soxhlet extract the remaining diesel oil, place the oil-absorbing bag in a 60°C oven to dry to constant weight, and separate the mixed solution of petroleum ether and diesel oil by distillation , recovery of diesel.

6) Repeat steps 3)-5).

The results are shown in Figure 5. From the experimental results, it can be seen that the material of the present invention can be recycled for many times, and the oil absorption rate changes little with the increase of the number of times.

6. Water/oil emulsion separation efficiency experiment of metal ion-polybenzoxazine micro-nanospheres:

1) Spread M ⁺ -polybenzoxazine micro-nanospheres evenly between two pieces of circular nylon cloth to form a filter layer.

2) Add 100ml of liquid oil, 1ml of ultrapure water, and 0.1g of Span 80 into a 250ml narrow-mouth bottle, and stir for 24 hours to form a water-in-oil emulsion with a droplet diameter of 8-20μm.

3) Filter the emulsion through the filter layer, and measure the water content of the filtrate with a Karl Fischer moisture analyzer.

The results are shown in Fig. 6. From the experimental results, it can be seen that the material of the present invention has a high separation efficiency for the water/oil emulsion, and the separation rate is over 90%.

Claims (4)

1. The use of metal ion-polybenzoxazine micro-nanospheres as an oil-water separation material. The metal ion-polybenzoxazine micro-nanospheres are polymerized by benzoxazine and metal ions to generate metal ions- Polybenzoxazine micelles are prepared by solidifying the micelles by the reverse phase suspension method. 2. The use of metal ion-polybenzoxazine micro-nanospheres as an oil-water separation material as claimed in claim 1, characterized in that: the preparation method of said metal ion-polybenzoxazine micro-nanospheres comprises the following steps: 1) Mix benzoxazine and metal ion at a molar ratio of 5: (0.2-1), dissolve in an organic solvent, and stir ultrasonically at room temperature to obtain metal ion-polybenzoxazine micelles; 3) Using glycerin or silicone oil as a medium, the metal ion-polybenzoxazine micelles are solidified at 120-240° C., and the metal ion-polybenzoxazine micro-nanospheres are obtained after the medium is eluted. 3. The use of metal ion-polybenzoxazine micronanospheres as an oil-water separation material according to claim 2, characterized in that: the molar ratio of the benzoxazine to the metal ion is 5:0.5. 4. The use of metal ion-polybenzoxazine micro-nanospheres as an oil-water separation material according to any one of claims 1-3, characterized in that: the metal ion is Fe ³⁺ or Zn ²⁺ or Cu ^{2 +} .