CN115282789A - A kind of ABS-Ni composite separation membrane and its preparation method and application - Google Patents

Abstract

The invention relates to an ABS-Ni composite separation membrane and a preparation method and application thereof. The preparation method comprises the following steps: performing pretreatment including etching treatment on the ABS membrane, and immersing the pretreated ABS membrane in an aqueous solution of silver ions; An ABS-Ag film adsorbed with silver ions is obtained; the ABS-Ag film is immersed in an electroless nickel plating solution, and an ABS-Ni composite separation film is prepared through an electroless plating reaction. The invention prepares the ABS-Ni composite separation membrane by chemically plating a metal nickel layer on the 3D printing base membrane, so that it has excellent antifouling performance, hydrophilicity and underwater superoleophobicity. In addition, the preparation method has the advantages of simple operation, mild reaction process conditions, no energy consumption, strong adaptability, and easy realization of large-scale industrial application.

Description

A kind of ABS-Ni composite separation membrane and its preparation method and application

technical field

The invention relates to the technical field of polymer membrane surface modification, in particular to an ABS-Ni composite separation membrane and a preparation method and application thereof.

Background technique

Membrane technology has become the most widely used technology for oil-water separation due to its advantages of high separation efficiency, low cost and no secondary pollution. However, the membrane fouling problem and the constraints of the membrane preparation process have become a huge challenge in the membrane application process. Membrane fouling can lead to a drastic reduction in filtration rate, which increases energy consumption and costs. The common membrane preparation process is restricted by the mutual restriction of selectivity and permeability, which limits the separation efficiency of the membrane. Therefore, there is an urgent need in this field to improve the traditional film-making process and develop a better alternative process. At present, nano-electrospun membranes and two-dimensional layered structure membranes, which have achieved rapid development, have made some progress in the preparation and modification of membranes, and 3D printing technology has gradually been applied in membrane preparation.

3D printing technology can precisely design and control the macroscopic structure of the film by computer, and has the advantage of realizing one-time film formation. 3D printing technologies are mainly divided into four categories: photopolymerization, powder fusion, material extrusion, and sheet lamination. Fused deposition manufacturing (FDM) is widely used because of its low cost, simple operation, and high speed. FDM technology extrudes thermoplastic filaments on the tray according to the coordinates preset by the software, and forms a film structure after stacking two layers of plastic filaments.

As a model material for 3D printing technology, acrylonitrile-butadiene-styrene (ABS) has the common properties of the three components and is a non-toxic material with good impact resistance, heat resistance, low temperature resistance, etc. . Therefore, compared with traditional commercial membranes, 3D printed membranes not only have the advantages of being tougher and stronger in acid and alkali resistance, but also significantly reduce toxicity. 3D printed membranes bring new possibilities for material and structural optimization of commercial membranes. However, 3D printed membranes cannot be directly used as separation membranes, and they still need to be modified to improve their hydrophilicity, electrical conductivity, and anti-pollution properties.

Contents of the invention

The purpose of the present invention is to provide an ABS-Ni composite separation membrane and its preparation method and application. The ABS-Ni composite separation membrane provided by the present invention has hydrophilic and underwater super-oleophobic properties, and can realize high-efficiency oil-water separation through gravity .

For this reason, in the first aspect, the invention provides a kind of preparation method of ABS-Ni composite separation membrane, it may further comprise the steps:

Perform the following pretreatments on the ABS film: perform etching on the ABS film;

Immersing the pretreated ABS film in an aqueous solution of silver ions to obtain an ABS-Ag film adsorbed with silver ions;

The ABS-Ag membrane is immersed in an electroless nickel plating solution, and undergoes an electroless plating reaction to prepare an ABS-Ni composite separation membrane.

Further, the ABS film can be prepared by 3D printing, such as fused deposition technology 3D printing.

Further, the ABS membrane has a pore size of 100-400 μm, such as 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm and the like.

Further, in the pretreatment step, before the etching treatment, it also includes: degreasing the ABS film with an alkaline solution.

Further, the alkaline solution includes one or a combination of two or more of sodium hydroxide solution, potassium hydroxide solution, and lithium hydroxide solution.

In some embodiments, the alkaline solution includes: sodium carbonate, sodium phosphate, sodium hydroxide and an emulsifier.

Further, in the alkaline solution, the concentration of the sodium carbonate is 30-40g/L, such as 30g/L, 35g/L, 40g/L, etc.; the concentration of the sodium phosphate is 20-30g/L, such as 20g/L, 25g/L, 30g/L, etc.; the concentration of the sodium hydroxide is 20-30g/L, such as 20g/L, 25g/L, 30g/L, etc.

In a certain embodiment, the emulsifier is an OP emulsifier, and in the alkaline solution, the concentration of the OP emulsifier is 0.2-0.5% (V/V), such as 0.2%, 0.3%, 0.4%, 0.5% etc.

Further, the reaction temperature of the pretreatment is 60-80°C, such as 60°C, 70°C, 80°C, etc.

Further, the reaction time of the pretreatment is 5-25 minutes, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes and so on.

Further, the solution used for the etching treatment includes potassium permanganate solution.

In some embodiments, the solution used for the etching treatment includes: potassium permanganate, phosphoric acid, sulfuric acid.

Further, in the solution used for the etching treatment, the concentration of the potassium permanganate is 75-85g/L, such as 75g/L, 80g/L, 85g/L, etc.; the concentration of the phosphoric acid is 0.5- 2% (V/V), such as 0.5%, 1%, 1.5%, 2% etc.; the concentration of said sulfuric acid is 0.5-2% (V/V), such as about 0.5%, 1%, 1.5%, 2% %Wait.

In another embodiment, the solution used for the etching treatment is prepared according to the following steps: slowly add phosphoric acid to the potassium permanganate solution, and stir well to obtain liquid A; prepare the sulfuric acid solution as liquid B; The B solution is slowly poured into the A solution and constant volume.

Further, the silver ion solution is a silver nitrate solution or a silver chloride solution.

Further, the concentration of silver ions in the silver ion solution is 5-15mmol/L, such as 5mmol/L, 8mmol/L, 9.4mmol/L, 10mmol/L, 15mmol/L and the like.

According to the technical scheme of the present invention, the silver ions adsorbed by the ABS film will serve as catalysts for subsequent electroless plating. The reaction of adsorbing silver ions can be carried out at room temperature.

Further, the time for the pretreated ABS film to be immersed in the silver ion aqueous solution is more than 40 minutes, such as 40 minutes, 50 minutes, 60 minutes, 100 minutes, 120 minutes and the like.

Further, the electroless nickel plating solution includes: nickel salt, metal complexing agent and reducing agent.

Further, the nickel salt is one or a combination of two or more of nickel sulfate, nickel chloride, nickel acetate, nickel hypophosphite, and nickel sulfamate.

Further, the metal complexing agent is one or a combination of sodium edetate and sodium pyrophosphate.

Further, the reducing agent is dimethylaminoborane.

Further, the electroless nickel plating solution also includes ammonia water.

In some embodiments, the electroless nickel plating solution includes nickel sulfate, sodium pyrophosphate, ammonia water and dimethylaminoborane.

In other embodiments, the electroless nickel plating solution includes nickel sulfate hexahydrate, sodium pyrophosphate decahydrate, ammonia water, and dimethylaminoborane.

In some further embodiments, in the electroless nickel plating solution, the concentration of nickel sulfate hexahydrate is 20-30g/L, such as 20g/L, 25g/L, 30g/L, etc.; the concentration of sodium pyrophosphate decahydrate is 45-55g/L, such as 45g/L, 50g/L, 55g/L, etc.; the concentration of ammonia is 1-2%, such as about 1%, 1.1%, 1.2%, 1.5%, 2%, etc.; dimethyl The concentration of aminoborane is 1-2g/L, such as 1g/L, 1.5g/L, 2g/L, etc.

Further, the temperature of the electroless plating reaction is 20-40°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, etc.; the time of the electroless plating reaction is 3-10min, such as 3min, 4min, 5min , 6min, 8min, 10min, etc.

The second aspect of the present invention provides an ABS-Ni composite separation membrane prepared by the preparation method described in the present invention.

The third aspect of the present invention provides the application of the ABS-Ni composite separation membrane in oil-water separation.

Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

(1) The present invention prepares an ABS-Ni composite separation membrane by chemically plating a metal nickel layer on the 3D printing base membrane, so that it has excellent anti-fouling properties, hydrophilicity and underwater superoleophobicity, and is resistant to oil under gravity. When the wastewater is separated, the interception rate of oily wastewater can reach 99.78% only under the action of gravity, and the flux can reach 53366L m ² h ^-1 .

(2) The present invention uses a 3D printer to directly print out the ABS base film, only needs to input the design model into the printer, and does not need manual operation to make the film, and can obtain a film with neatly arranged film pores and regular shapes. The method is simple and fast for film production, simple in operation method, low in cost, and has obvious promotion advantages.

(3) The present invention realizes the adsorption of silver ions through a simple immersion method, and then, under the catalytic action of silver ions, in situ reduces metal nickel on the ABS base film, and successfully coats nickel on the 3D printed ABS film. The method has simple operation, mild reaction process conditions, no energy consumption, strong adaptability, and easy realization of large-scale industrial application.

Description of drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiment. The drawings are only for the purpose of illustrating a preferred embodiment and are not to be considered as limiting the invention. In the attached picture:

Fig. 1: the physical picture of ABS membrane and the ABS-Ni composite separation membrane provided by the present invention; a is the ABS membrane, b is the ABS-Ni composite separation membrane;

Fig. 2: the scanning electron micrograph of ABS membrane and the ABS-Ni composite separation membrane provided by the present invention; c and e are ABS membrane, and d and f are ABS-Ni composite separation membrane;

Figure 3: Flux comparison of ABS membranes with different pore sizes and ABS-Ni composite separation membranes under the action of gravity;

Figure 4: Comparison of the oil-water separation efficiency of ABS membranes with different pore sizes and ABS-Ni composite separation membranes under the action of gravity.

Detailed ways

Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided for more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.

Example 1

The present embodiment provides a kind of ABS-Ni composite separation membrane, and its preparation method is as follows:

Industrial-grade 3D printers (F170, Stratasys, USA) printed ABS membranes with uniform and regular membrane pores through fusion deposition technology, and printed ABS membranes with the following three pore sizes: 240×400 μm, 100×240 μm, 100×150 μm; Membranes with three pore sizes were prepared according to the following steps to prepare corresponding ABS-Ni composite separation membranes.

(1) Pretreatment

(1) Degreasing treatment: Dissolve 35g Na ₂ CO ₃ , 25g Na ₃ PO ₄ , 25g NaOH, and 3mL OP emulsifier in 1L of water to prepare an alkaline solution; immerse the ABS film in the alkaline solution at 70 Under the condition of ℃, react for 5 minutes.

( ₂ ) Preparation of etching solution: Dissolve 40g of KMnO4 in pure water, slowly add 5mL of phosphoric acid, and stir well to make liquid A; slowly pour 5mL of concentrated sulfuric acid into 50mL water, stir well to make liquid B; Solution B was slowly poured into solution A and the volume was adjusted to 500mL to prepare an etching solution.

(3) Etching treatment: immerse the degreased ABS film in the etching solution, and react at 70° C. for 15 minutes. Mix 28g of H ₂ C ₂ O ₄ with 25mL of H ₂ SO ₄ and set the volume to 1L, immerse the etched ABS film in it for neutralization reaction, take it out and clean it with pure water.

(2) Electroless nickel plating

(1) Adsorption of silver ions: The pretreated ABS film was immersed in a 1.597g/L AgNO ₃ solution, and reacted at 25°C for 40 minutes to allow the ABS film to adsorb silver ions to prepare an ABS-Ag film.

(2) Preparation of electroless plating solution: 25g NiSO ₄ 6H ₂ O, 50g Na ₄ P ₂ O ₇ 10H ₂ O, 45mL ammonia water with a concentration of 28%, and 1.5g C ₂ H ₁₀ BN were dilute to 1L to prepare an electroless plating solution.

(3) Electroless plating reaction: immerse the ABS-Ag film in the electroless plating solution for electroless plating reaction, and react at 25° C. for 4 minutes to prepare an ABS-Ni composite separation membrane. The ABS-Ni composite separation membrane was fully washed and stored in ionized water.

The physical picture of the ABS membrane and the ABS-Ni composite separation membrane prepared above is shown in Figure 1, wherein Figure 1a is the ABS membrane, and Figure 1b is the ABS-Ni composite separation membrane. According to Figure 1, the ABS film presents an opaque ivory color, while the ABS-Ni composite separation film presents a silvery white metallic luster.

The surface morphology of the membrane was further studied by scanning electron microscope imaging. As shown in Figure 2, the surface morphology of the ABS membrane is relatively smooth (Figure 2c and Figure 2e), while the surface of the ABS-Ni composite separation membrane is relatively rough (Figure 2d and Figure 2f ); and it can be clearly seen that the surface of the ABS-Ni composite separation membrane is evenly covered with metallic nickel particles, indicating that the metallic nickel layer has been successfully plated on the ABS film surface.

Example 2

The present embodiment provides a kind of ABS-Ni composite separation membrane, and its preparation method is as follows:

Industrial-grade 3D printers (F170, Stratasys, USA) printed ABS membranes with uniform and regular membrane pores through fusion deposition technology, and prepared corresponding ABS-Ni composite separation membranes according to the following steps.

(1) Pretreatment

(1) Degreasing treatment: Dissolve 40g Na ₂ CO ₃ , 20g Na ₃ PO ₄ , 30g NaOH, and 5mL OP emulsifier in 1L of water to prepare an alkaline solution; soak the ABS film in the alkaline solution at 70 Under the condition of ℃, react for 5 minutes.

(2) Preparation of etching solution: dissolve 37.5g of KMnO ₄ in pure water, slowly add 8mL of phosphoric acid, and stir well to make liquid A; slowly pour 5mL of concentrated sulfuric acid into 50mL of water, stir evenly to make liquid B; Slowly pour liquid B into liquid A and set the volume to 500mL to prepare an etching solution.

(3) Etching treatment: immerse the degreased ABS film in the etching solution, and react at 70° C. for 15 minutes. Mix 28g of H ₂ C ₂ O ₄ with 25mL of H ₂ SO ₄ and set the volume to 1L, immerse the etched ABS film in it for neutralization reaction, take it out and clean it with pure water.

(2) Electroless nickel plating

(1) Adsorption of silver ions: immerse the pretreated ABS film in a 1.347g/L AgCl solution, and react at 25°C for 50 minutes to allow the ABS film to adsorb silver ions to prepare an ABS-Ag film.

(2) Preparation of electroless plating solution: 30g NiSO ₄ 6H ₂ O, 55g Na ₄ P ₂ O ₇ 10H ₂ O, 45mL ammonia water with a concentration of 28%, 2g C ₂ H ₁₀ BN were adjusted to 1L with pure water , to prepare an electroless plating solution.

(3) Electroless plating reaction: immerse the ABS-Ag film in the electroless plating solution for electroless plating reaction, react at 30° C. for 5 minutes, and then prepare the ABS-Ni composite separation membrane. The ABS-Ni composite separation membrane was fully washed and stored in ionized water.

Example 3

The present embodiment provides a kind of ABS-Ni composite separation membrane, and its preparation method is as follows:

Industrial-grade 3D printers (F170, Stratasys, USA) printed ABS membranes with uniform and regular membrane pores through fusion deposition technology, and prepared corresponding ABS-Ni composite separation membranes according to the following steps.

(1) Pretreatment

(1) Degreasing treatment: Dissolve 30g Na ₂ CO ₃ , 30g Na ₃ PO ₄ , 20g NaOH, and 5mL OP emulsifier in 1L of water to prepare an alkaline solution; soak the ABS film in the alkaline solution, at 70 Under the condition of ℃, react for 5 minutes.

( ₂ ) Preparation of etching solution: Dissolve 42.5g KMnO4 in pure water, slowly add 5mL of phosphoric acid, stir well to make liquid A; slowly pour 8mL of concentrated sulfuric acid into 50mL water, stir evenly to make liquid B; Slowly pour liquid B into liquid A and set the volume to 500mL to prepare an etching solution.

(3) Etching treatment: immerse the degreased ABS film in the etching solution, and react at 70° C. for 15 minutes. Mix 28g of H ₂ C ₂ O ₄ with 25mL of H ₂ SO ₄ and set the volume to 1L, immerse the etched ABS film in it for neutralization reaction, take it out and clean it with pure water.

(2) Electroless nickel plating

(1) Adsorption of silver ions: The pretreated ABS film was immersed in a 1.597g/L AgNO ₃ solution, and reacted at 25°C for 50 minutes to allow the ABS film to adsorb silver ions to prepare an ABS-Ag film.

(2) Preparation of electroless plating solution: 25g NiSO ₄ 6H ₂ O, 45g Na ₄ P ₂ O ₇ 10H ₂ O, 45mL ammonia water with a concentration of 28%, and 1g C ₂ H ₁₀ BN were adjusted to 1L with pure water , to prepare an electroless plating solution.

(3) Electroless plating reaction: immerse the ABS-Ag film in the electroless plating solution for electroless plating reaction, react at 30° C. for 5 minutes, and then prepare the ABS-Ni composite separation membrane. The ABS-Ni composite separation membrane was fully washed and stored in ionized water.

Experimental example

The ABS-Ni composite separation membrane prepared in Example 1 was subjected to the separation test of the oil-water mixture only under the action of gravity. The test results are shown in Figure 3 and Figure 4. According to the test results, the flux of the ABS-Ni composite separation membrane has been significantly improved compared with the ABS membrane. In terms of rejection rate, the rejection rate of the unmodified ABS membrane is 0% regardless of the pore size, which does not play any role in oil-water separation; while the modified ABS-Ni composite separation membrane has excellent performance in filtering oil-water separation. A good interception effect was achieved, especially after the ABS-Ni composite separation membrane was obtained by modifying the membrane with a pore size of 100×150 μm, the rejection rate was as high as 99.78% while the flux was as high as 53366L·m ^-2 h ^-1 .

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (10)

1. A preparation method of an ABS-Ni composite separation membrane is characterized by comprising the following steps:

the ABS film was pretreated as follows: etching the ABS film;

immersing the pretreated ABS film into a silver ion water solution to obtain an ABS-Ag film adsorbed with silver ions;

and (3) immersing the ABS-Ag film into a chemical nickel plating solution, and performing chemical plating reaction to obtain the ABS-Ni composite separation film.

2. The production method according to claim 1, wherein the ABS film is produced by 3D printing;

preferably, the pore size of the ABS film is 100-400 μm.

3. The method according to claim 1, wherein the preprocessing step further includes, before the etching treatment: carrying out oil removal treatment on the ABS film by using an alkaline solution;

preferably, the alkaline solution comprises one or a combination of more than two of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution;

preferably, the alkaline solution comprises: sodium carbonate, sodium phosphate, sodium hydroxide and an emulsifier.

4. The production method according to any one of claims 1 to 3, wherein the reaction temperature of the pretreatment is 60 to 80 ℃.

5. The production method according to claim 1, wherein the solution used for the etching treatment comprises a potassium permanganate solution;

preferably, the solution for the etching treatment includes: potassium permanganate, phosphoric acid, sulfuric acid;

preferably, in the solution for the etching treatment, the concentration of the potassium permanganate is 75-85g/L, the concentration of the phosphoric acid is 0.5-2% (V/V), and the concentration of the sulfuric acid is 0.5-2% (V/V).

6. The production method according to claim 1, wherein the silver ion solution is a silver nitrate solution or a silver chloride solution;

preferably, the concentration of silver ions in the silver ion solution is 5-15mmol/L;

preferably, the time for immersing the pretreated ABS film into the silver ion aqueous solution is more than 40 min.

7. The method of claim 1, wherein said electroless nickel plating solution comprises: nickel salt, metal complexing agent and reducing agent;

preferably, the nickel salt is one or the combination of more than two of nickel sulfate, nickel chloride, nickel acetate, nickel hypophosphite and nickel sulfamate;

preferably, the metal complexing agent is one or a combination of two of sodium ethylene diamine tetracetate and sodium pyrophosphate;

preferably, the reducing agent is dimethylaminoborane;

preferably, the electroless nickel plating solution further comprises ammonia.

8. The method according to claim 1, wherein the electroless plating reaction is carried out at a temperature of 20 to 40 ℃ for 3 to 10min.

9. An ABS-Ni composite separation membrane, characterized in that the ABS-Ni composite separation membrane is prepared by the preparation method of any one of claims 1 to 8.

10. The ABS-Ni composite separation membrane prepared by the preparation method of any one of claims 1 to 8 is applied to oil-water separation.

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