CN105148564A - Preparation method for super-hydrophilic and super-oleophobic oil-water separation net film - Google Patents

Abstract

The invention discloses a preparation method of a superhydrophilic and superoleophobic oil-water separation mesh. The method comprises the following steps: (1) pretreating the stainless steel mesh; (2) dissolving a certain amount of F127 and CTAB in 20 mL of Water ethanol, in this solution, add nitric acid and aluminum isopropoxide, dry after stirring to obtain powder, (3) dissolve powder and tetraethylenepentamine in ethanol solution and stir to prepare aluminum oxide sol; (4) The stainless steel mesh coated with zinc oxide film is dipped in aluminum oxide sol and then dried, and then annealed after repeated dipping and drying for 2 to 8 times, which is the superhydrophilic and superoleophobic oil-water separation mesh of the present invention. The invention has simple process, and the prepared omentum has super-hydrophilic performance, good acid and alkali corrosion resistance, is suitable for large-scale production, and has wide application in the field of oil-water separation.

Description

A kind of preparation method of superhydrophilic and superoleophobic oil-water separation omentum

technical field

The invention belongs to the technical field of inorganic membrane materials, in particular to a preparation method of a superhydrophilic and superoleophobic oil-water separation membrane.

technical background

The frequent occurrence of offshore oil spill accidents and the massive discharge of oily sewage in national production and life have seriously affected the living environment of humans and other organisms. The development of an environmentally friendly, high-efficiency oil-water separation and low-cost oil-water separation material has become the focus of current research fields. Focus.

Due to its superhydrophilic and superoleophobic properties, the superhydrophilic and superoleophobic oil-water separation membrane can allow water to permeate the membrane and keep the oil on the surface to achieve the purpose of oil-water separation. The oil-repellent properties of the membrane It guarantees the cleanness of the omentum surface to the greatest extent, and is an anti-pollution and long-life oil-water separation omentum.

Contents of the invention

Based on this, the invention discloses a preparation method of a superhydrophilic and superoleophobic oil-water separation omentum, said method comprising the following steps:

S100, pretreating the stainless steel mesh so that it is coated with a zinc oxide film;

S200, preparing powder:

S2001, dissolving F127 and CTAB in a beaker filled with absolute ethanol, sealing the mouth of the beaker and stirring at room temperature with a magnetic stirrer to make the mixture uniform;

S2002. Open the mouth of the beaker, add nitric acid and aluminum isopropoxide to the solution stirred in step S2001, seal the mouth of the beaker and stir at room temperature with a magnetic stirrer;

S2003, drying the solution stirred in step S2002 into powder in a drying oven;

S300, preparing sol:

S3001, adding tetraethylenepentamine to absolute ethanol, and mixing uniformly at room temperature;

S3002. Add the powder obtained in step S2003 to the solution uniformly mixed in step S3001, and mix uniformly at room temperature to form a sol;

S400, preparing superhydrophilic and superoleophobic oil-water separation omentum:

S4001. Dip the stainless steel mesh coated with the zinc oxide film obtained in step S100 into the sol obtained in step S3002, pull it at a constant speed to form a uniform film layer, and dry it in a drying oven;

S4002. After treating the stainless steel mesh for 2-8 times according to the method described in step S4001, perform annealing treatment in a high-temperature furnace to obtain a superhydrophilic and superoleophobic oil-water separation mesh.

Detailed ways

Below in conjunction with specific embodiment the present invention is further described;

In one embodiment, the invention discloses a method for preparing a superhydrophilic and superoleophobic oil-water separation omentum, said method comprising the following steps:

S100, pretreating the stainless steel mesh so that it is coated with a zinc oxide film;

S200, preparing powder:

S2001, dissolving F127 and CTAB in a beaker filled with absolute ethanol, sealing the mouth of the beaker and stirring at room temperature with a magnetic stirrer to make the mixture uniform;

S2002. Open the mouth of the beaker, add nitric acid and aluminum isopropoxide to the solution stirred in step S2001, seal the mouth of the beaker and stir at room temperature with a magnetic stirrer;

S2003, drying the solution stirred in step S2002 into powder in a drying oven;

S300, preparing sol:

S3001, adding tetraethylenepentamine to absolute ethanol, and mixing uniformly at room temperature;

S3002. Add the powder obtained in step S2003 to the solution uniformly mixed in step S3001, and mix uniformly at room temperature to form a sol;

S400, preparing superhydrophilic and superoleophobic oil-water separation omentum:

S4001. Dip the stainless steel mesh coated with the zinc oxide film obtained in step S100 into the sol obtained in step S3002, pull it at a constant speed to form a uniform film layer, and dry it in a drying oven;

S4002. After treating the stainless steel mesh for 2-8 times according to the method described in step S4001, perform annealing treatment in a high-temperature furnace to obtain a superhydrophilic and superoleophobic oil-water separation mesh.

The multiple dipping described in this embodiment is to fully coat the surface of the stainless steel mesh with a zinc oxide film to prevent part of the coating from being leaked, and the number of times of coating is small and the coating is easy to leak; coating after each drying is also for the same purpose.

The purpose of sealing the mouth of the beaker in step S2001 of this embodiment is to prevent the volatilization of absolute ethanol and keep the concentration of the solute in the solution from being greatly deviated.

In this embodiment, after the stainless steel mesh is dipped and dried for many times, the sol forms a dense film on the outside of the stainless steel mesh coated with a zinc oxide film, and the dense film is transformed into an aluminum oxide film after annealing in step S4002. The aluminum film acts as superhydrophilic and superoleophobic.

The oil-water separation mesh prepared in this example is composed of a zinc oxide base layer and a low-surface-energy aluminum oxide modification layer, and the super-hydrophilic and super-oleophobic properties of the oil-water separation membrane are realized by using the low-surface-energy modification layer. The combination ability of the low surface energy modification layer and the stainless steel mesh is enhanced by using the double-layer composite film. The composite oil-water separation membrane composed of zinc oxide and aluminum oxide has good high temperature stability and acid and alkali corrosion resistance. The raw materials used are easy to obtain, and the process parameters need to be controlled during the preparation. It has a wide range of applications in the field of oil-water separation. Applications.

The raw materials used in the method described in this example are readily available, and the process parameters required to be controlled are less, and the prepared oil-water separation membrane has good high temperature stability and acid and alkali corrosion resistance.

In one embodiment, the S100 includes:

S1001, impregnating the cleaned stainless steel mesh in a zinc acetate solution;

S1002, taking out the impregnated stainless steel mesh and putting it into a drying oven for drying;

S1003. Repeat dipping and drying the stainless steel mesh for 2 to 8 times according to the method described in step S1001 and step S1002, and then put it into a high-temperature furnace for annealing treatment to obtain a stainless steel mesh coated with a zinc oxide film;

Wherein, the concentration of the zinc acetate solution in the step S1001 is 0.1-0.5mol/L; the mesh number of the stainless steel mesh is 100-600 mesh; the time for the stainless steel mesh to be immersed in the zinc acetate solution each time is 10-30s .

More preferably, the zinc acetate solution is dissolved in 50mL deionized water by 1.10g of zinc acetate, fully stirred to obtain, the mesh number of the stainless steel mesh is 100 mesh, and the time for each dipping of the stainless steel mesh in the sodium acetate solution is 15s.

In one embodiment, in the step S1002, the stainless steel mesh is dried in a drying oven for 10-50 minutes, and the temperature of the drying oven is 60-80°C during drying.

More preferably, in the step S1002, the stainless steel mesh is dried in a drying oven for 40 minutes, and the temperature of the drying oven is 70° C. during drying.

In this embodiment, the selection of drying time and impregnation are related to the times of drying.

In one embodiment, in the step S1003, the annealing temperature of the stainless steel mesh is placed in a high temperature furnace for annealing treatment is 350-450° C., and the annealing time is 0.5-2 hours.

The reason for annealing the stainless steel mesh in this embodiment is to homogenize the chemical composition of the stainless steel mesh, remove residual stress, and obtain expected physical properties.

In one embodiment, the ratio of each material when preparing the powder in step S200 is: F127 and CTAB are 0.5-2.5g, nitric acid is 0.5-2.5mL, nitric acid wt% is 67%, aluminum isopropoxide is 1.02 ～3.06g, 20ml of absolute ethanol; when preparing powder, the order of adding raw materials is: F127, CTAB, nitric acid and aluminum isopropoxide.

In one embodiment, the mass ratio of F127 and CTAB in the step S2001 is 1:1-1:4.

More preferably, the mass ratio of F127 and CTAB in the step S2001 is 1:2.

In one embodiment, the time for stirring at room temperature in step S2002 is 3-8 hours, and the temperature for drying the solution stirred in step S2002 in a drying oven in step S3003 is 60-80°C.

In one embodiment, the step S3001 specifically includes adding 1-2 g of tetraethylenepentamine into 10 ml of ethanol, and stirring at room temperature for 10-50 min to mix evenly;

Step S3002 specifically includes adding 1.5-2.5 g of the powder obtained in step S2003 to the solution uniformly mixed in step S3001, stirring at room temperature for 6-10 hours and mixing uniformly to obtain a sol.

More preferably, the step S3001 includes adding 1.5 g of tetraethylenepentamine into 10 ml of ethanol, and then stirring for 0.5 h;

Step S3002 includes adding 2 g of the powder obtained in step S2003 to the solution stirred in step S3001, and stirring at room temperature for 8 hours to obtain a sol.

In one embodiment, in the step S4001, the time for immersing the pretreated stainless steel mesh obtained in the step S1003 in the sol obtained in the step S3002 is 2-10 s, and the speed of pulling at a uniform speed is 0.1-5 cm/ s, the drying temperature in a drying oven is 60-80°C.

In one embodiment, the soaking time in the sol in the step S4001 is 10-30s;

In the step S4002, when the stainless steel mesh is annealed in a high-temperature furnace, the annealing temperature is 250-350° C., and the annealing time is 0.5-2 hours.

In one embodiment, the method of the present invention comprises the following steps:

1) Weigh 1.10g of zinc acetate and dissolve it in 50mL of deionized water, stir well to obtain a zinc acetate solution, dip a clean stainless steel mesh (100 mesh) in the zinc acetate solution for 10s, take it out and dry it in a drying oven at 60°C for 30min , repeat dipping and drying twice, place the stainless steel mesh after repeated dipping and drying in a high-temperature furnace at 350°C for 0.5h;

2) Weigh 0.25g of F127 and 0.25g of CTAB and dissolve them in 20mL of absolute ethanol, stir for 3 hours, add 0.5mL of nitric acid (wt% = 67%) and 1.02g of aluminum isopropoxide to the above solution in turn, and put the beaker Stir at room temperature with the mouth sealed, and dry into powder in a drying oven at 60°C;

3) Weigh 1 g of tetraethylenepentamine and add it to 10 g of ethanol, stir at room temperature for 0.5 h, add 2 g of the powder obtained in step 2) to the above solution, and stir at room temperature for 6 h to form a sol;

4) Dip the stainless steel mesh coated with zinc oxide film obtained in step 1) into the sol obtained in step 3) for 2 seconds, pull it upward at a constant speed of 0.1cm/s to form a uniform film layer, and dry it at 60°C Dry in the oven for 30 minutes, repeat the above impregnation and drying process twice, and then anneal in a high-temperature furnace at 250°C for 0.5 hours to prepare a superhydrophilic and superoleophobic oil-water separation mesh on the stainless steel mesh.

In one embodiment, the method of the present invention comprises the following steps:

1) Weigh 3.30g of zinc acetate and dissolve it in 50mL of deionized water, stir well to obtain a zinc acetate solution, dip a clean stainless steel mesh (350 mesh) in the zinc acetate solution for 20s, take it out and dry it in a drying oven at 70°C for 30min , repeated impregnation and drying 5 times, and placed the stainless steel mesh after repeated impregnation and drying in a high-temperature furnace at 400 ° C for 1 hour;

2) Weigh 0.30g of F127 and 1.20g of CTAB and dissolve them in 20mL of absolute ethanol, stir for 5h, add 1.5mL of nitric acid (wt% = 67%) and 2.04g of aluminum isopropoxide to the above solution in turn, and put the beaker Stir at room temperature with the mouth sealed, and dry into powder in a drying oven at 70°C;

3) Weigh 1.5 g of tetraethylenepentamine and add it to 10 g of ethanol, stir at room temperature for 0.5 h, add 2 g of the powder obtained in step 2) to the above solution, and stir at room temperature for 8 h to form a sol;

4) Dip the stainless steel mesh coated with zinc oxide film obtained in step 1) into the sol obtained in step 3) for 6 seconds, and pull it upward at a constant speed at a speed of 2.5cm/s to form a uniform film layer, and dry it at 70°C Dry in the oven for 30 minutes, repeat the above impregnation and drying process 5 times, and then anneal in a high-temperature furnace at 300 ° C for 1 hour to prepare a superhydrophilic and superoleophobic oil-water separation mesh on the stainless steel mesh.

In one embodiment, the method of the present invention comprises the following steps:

1) Weigh 5.50g of zinc acetate and dissolve it in 50mE deionized water, stir well to obtain a zinc acetate solution, dip a clean stainless steel mesh (600 mesh) in the zinc acetate solution for 30s, take it out and dry it in a drying oven at 80°C for 30min , repeated impregnation and drying 8 times, and placed the stainless steel mesh after repeated impregnation and drying in a high-temperature furnace at 450 ° C for 2 hours;

2) Weigh 0.5g of F127 and 2.00g of CTAB and dissolve them in 20mL of absolute ethanol, stir for 8h, add 2.5mE nitric acid (wt% = 67%) and 3.06g of aluminum isopropoxide to the above solution in turn, put the beaker Stir at room temperature with the mouth sealed, and dry into powder in an oven at 80°C;

3) Weigh 2.0 g of tetraethylenepentamine and add it to 10 g of ethanol, stir at room temperature for 0.5 h, add 2 g of the powder obtained in step 2) to the above solution, and stir at room temperature for 10 h to form a sol;

4) Immerse the stainless steel mesh coated with zinc oxide film obtained in step 1) in the sol obtained in step 3) for 10s, and pull it upward at a constant speed at a speed of 5cm/s to form a uniform film layer. After drying in medium for 30 min, repeating the above impregnation and drying process 8 times, annealing in a high-temperature furnace at 350°C for 2 h, a superhydrophilic and superoleophobic oil-water separation mesh was prepared on the stainless steel mesh.

The present invention has been described in detail above, and specific examples have been used herein to illustrate the principles and implementation modes of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea; meanwhile, for the technical field For those skilled in the art, according to the idea of the present invention, there will be changes in the specific implementation and application scope. In summary, the contents of this specification should not be construed as limiting the present invention.

Claims (10)

1. a preparation method for the oil-water separation mesh film of super hydrophilic and super oleophobic, is characterized in that: said method comprising the steps of:

S100, pretreatment stainless (steel) wire, make it to be coated with Zinc oxide film;

S200, prepare powder:

S2001, F127 and CTAB be dissolved into and be equipped with in the beaker of absolute ethyl alcohol, the sealing of beaker mouth is at room temperature carried out stirring to make to mix with magnetic stirring apparatus;

S2002, beaker mouth to be opened, in the solution after stirring in step S2001, add nitric acid and aluminium isopropoxide, the sealing of beaker mouth is at room temperature stirred with magnetic stirring apparatus;

S2003, by step S2002 stir after solution in drying box, be dried to powder;

S300, prepare colloidal sol:

S3001, TEPA to be joined in absolute ethyl alcohol, and at room temperature mix;

S3002, mix in step S3001 after solution in add the powder obtained in step S2003, and at room temperature mix formation colloidal sol;

S400, prepare the oil-water separation mesh film of super hydrophilic and super oleophobic:

Flood in S4001, the colloidal sol of the stainless (steel) wire being coated with Zinc oxide film gained in step S3002 that step S100 is obtained, at the uniform velocity lift, form uniform rete, and dry in drying box;

S4002, by described stainless (steel) wire according to after the method process described in step S4001 2 ~ 8 times, in high temperature furnace, carry out annealing in process, just obtain the oil-water separation mesh film of super hydrophilic and super oleophobic.

2. method according to claim 1, is characterized in that: preferred, described S100 comprises:

S1001, the stainless (steel) wire after clean to be flooded in zinc acetate solution;

S1002, the stainless (steel) wire after dipping taken out and puts into drying box and carry out drying;

S1003, by stainless (steel) wire according to after the method repeated impregnations described in step S1001 and step S1002 and dry 2 ~ 8 times, put into high temperature furnace and carry out the stainless (steel) wire that annealing in process obtains being coated with Zinc oxide film;

Wherein, the concentration of the zinc acetate solution in described step S1001 is 0.1 ~ 0.5mol/L; The order number of stainless (steel) wire is 100 ~ 600 orders; The time that described stainless (steel) wire floods at every turn in zinc acetate solution is 10 ~ 30s.

3. method according to claim 1, is characterized in that: time 10 ~ 50min that in described step S1002, stainless (steel) wire is dry in drying box, and time dry, the temperature of drying box is 60 ~ 80 DEG C.

4. method according to claim 1, is characterized in that: in described step S1003, stainless (steel) wire puts into the annealing temperature that high temperature furnace carries out annealing in process is 350 ~ 450 DEG C, and annealing time is 0.5 ~ 2h.

5. method according to claim 1, it is characterized in that: the proportioning preparing each material during powder in described step S200 is: F127 and CTAB is 0.5 ~ 2.5g, nitric acid is 0.5 ~ 2.5mL, and nitric acid wt% is 67%, aluminium isopropoxide is 1.02 ~ 3.06g, and absolute ethyl alcohol is 20ml; When preparing powder, raw material addition sequence is followed successively by: F127, CTAB, nitric acid and aluminium isopropoxide.

6. method according to claim 5, is characterized in that: in described step S2001, F127 and CTAB quality proportioning is 1: 1 ~ 1: 4.

7. method according to claim 1, is characterized in that: the time of at room temperature carrying out in described step S2002 stirring is 3 ~ 8h, is 60 ~ 80 DEG C by temperature dry in drying box for the solution after stirring in step S2002 in described step S3003.

8. method according to claim 1, is characterized in that: described step S3001 specifically comprises and being joined in 10ml ethanol by the TEPA of 1 ~ 2g, and at room temperature stirs 10 ~ 50min to mix;

Step S3002 at room temperature stirs 6 ~ 10h and mixes, obtain colloidal sol after specifically comprising the 1.5 ~ 2.5g powder adding in the solution after mixing in step S3001 and obtain in step S2003.

9. method according to claim 1, it is characterized in that: be 2 ~ 10s by time of flooding in the colloidal sol of pretreated stainless (steel) wire gained in step S3002 of gained in step S1003 in described step S4001, speed when at the uniform velocity lifting is 0.1 ~ 5cm/s, and temperature dry in drying box is 60 ~ 80 DEG C.

10. method according to claim 1, is characterized in that: annealing temperature when stainless (steel) wire carries out annealing in process in high temperature furnace in described step S4002 is 250 ~ 350 DEG C, and annealing time is 0.5 ~ 2h.