CN110354699A - A kind of preparation method of the modified plural gel seperation film of transient state hydrogel and its application method in dye wastewater - Google Patents

Abstract

The preparation method and its application method in dye wastewater that the present invention provides a kind of plural gel seperation film of transient state hydrogel modification, specific steps are as follows: copper nitrate is added in ethylene glycol, stirring is added dropwise carbon nano-tube solution, obtains the carbon nano-tube solution of supported copper to dissolving；Methacrylic acid monomer and polyethylene glycol are added in deionized water, stirs evenly, the carbon nano-tube solution of supported copper is added, continue to stir evenly, initiator is added, two-dimensional surface carrier is sufficiently impregnated wherein, to be passed through nitrogen, heating sealing reaction, takes out, obtains the plural gel seperation film of cupric coordination；The plural gel seperation film of cupric coordination is handled through Frozen-thawed cycled, obtains the modified plural gel seperation film of transient state hydrogel.After the modified plural gel seperation film absorption waste water from dyestuff of transient state hydrogel, stands, filter at room temperature, obtain the sol-gel modified plural gel seperation film of removal dyestuff；The sol-gel modified plural gel seperation film for removing dyestuff is handled through turbula shaker, obtains the modified plural gel seperation film of regeneration transient state hydrogel.

Description

A kind of preparation method of transient hydrogel modified composite gel separation membrane and its dyeing Application method in raw sewage

technical field

The invention belongs to the technical field of dye sewage treatment, and in particular relates to a preparation method of a transient hydrogel-modified composite gel separation membrane and an application method thereof in dye sewage.

Background technique

Dyestuff is an important raw material in the textile field, which brings colorful visual enjoyment to textiles. However, most of the dyestuffs are aromatic compounds synthesized from petrochemical products as the main raw materials. They have stable chemical properties, low biodegradability, and remain in the environment. It also has a serious impact on human beings and their ecological environment. Therefore, the removal of dye pollution in water in the environment of industrial dye wastewater treatment machines has attracted more and more attention.

At present, the treatment methods of industrial dye wastewater include biodegradation and physicochemical methods such as flocculation, catalytic oxidation, membrane filtration and adsorption. Among them, membrane filtration, especially nanofiltration membrane, has low operating pressure and good separation performance for small molecules , but membrane separation can easily lead to irreversible membrane fouling. Therefore, the research on new hydrogel membrane separation technology has good prospects.

Chinese invention patent application (CN108704495A) discloses a method for preparing a carboxylated titanium dioxide/calcium alginate composite gel separation membrane filtration membrane. Toluene solvent is added to the suction filter bottle, carboxylic acid is added, and four tetrafluoroethylene is rapidly added dropwise under the condition of nitrogen flow. Titanium chloride, add deionized water dropwise until precipitation occurs, heat and stir at 30-90 ° C for one hour, heat and concentrate, wash and dry to obtain carboxylated titanium dioxide, then add deionized water to start stirring, add enhancer, and seaweed After the solution is completely dissolved, the obtained solution is vacuum defoamed to obtain a film casting liquid. The film casting liquid is poured on a dry and clean glass sheet, and a uniform film is scraped with a film scraping rod. Then, the membrane together with the glass sheet is immersed in a calcium chloride aqueous solution coagulation bath to obtain a carboxylated titanium dioxide/calcium alginate composite gel separation membrane filtration membrane. The carboxylated titanium dioxide/calcium alginate composite gel separation membrane filter membrane is repeatedly rinsed with deionized water to obtain the carboxylated titanium dioxide/calcium alginate composite gel separation membrane filter membrane. The carboxylated titanium dioxide/calcium alginate composite gel separation membrane filtration membrane prepared by this method is used to intercept dyes with different molecular weights. 10%-30%, the breaking strength can reach 0.5-2MPa.

Chinese invention patent CN105107389B discloses a preparation method of a gel composite separation membrane, which is to graft the membrane-forming polymer, cross-linked polyacrylamide/cross-linked sodium polyacrylate/cross-linked starch into sodium polyacrylate gel polymer , The porogen is mixed with the solvent, fully dissolved by mechanical stirring, defoamed and filtered to obtain the casting liquid, which is coated or extruded through a film forming machine, immersed in a pure water bath to solidify and form, to obtain the primary polymer The primary polymer membrane is fully washed in deionized water, and then dried in the air to obtain a gel composite microfiltration membrane, ultrafiltration membrane or nanofiltration membrane. It can be known from the above prior art that the gel composite separation membrane has broad application prospects in the field of membrane separation such as dye separation.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a preparation method of a transient hydrogel-modified composite gel separation membrane and its application method in dye sewage. The transient hydrogel-modified composite membrane prepared by the present invention Gel separation membranes contain mechanically enhanced hydrogels and transient hydrogels, in which the transient hydrogels transform into sols upon standing at room temperature. From sol to transient hydrogel, the adsorbed dyes can be released for the reuse of dye separation membranes.

For solving the above-mentioned technical problems, the technical scheme of the present invention is:

A preparation method of a composite gel separation membrane modified by transient hydrogel is characterized in that: comprising the following steps:

(1) adding copper nitrate into ethylene glycol, stirring to dissolve, dripping carbon nanotube solution to obtain a copper-loaded carbon nanotube solution;

(2) adding the methacrylic acid monomer and polyethylene glycol into deionized water, stirring uniformly, adding the copper-loaded carbon nanotube solution prepared in step (1), continuing to stir uniformly, adding an initiator, and mixing the two-dimensional planar carrier Fully immersed in it, introduced nitrogen gas, heated and sealed for reaction, and taken out to obtain a copper-coordinated composite gel separation membrane;

(3) subjecting the copper-coordinated composite gel separation membrane prepared in step (2) to freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane.

As a preference of the above technical solution, in the step (1), the mass ratio of copper nitrate and carbon nanotubes is 2-3:1.

As a preference of the above technical solution, in the step (1), the volume content of ethylene glycol in the copper-loaded carbon nanotube solution is 75-85%.

As a preference of the above technical solution, in the step (2), the mass ratio of methacrylic acid monomer and polyethylene glycol is 0.3-0.4:1.

As a preference of the above technical solution, in the step (2), the two-dimensional plane carrier is a fabric, a nanofiber film or a polymer film.

As a preference of the above technical solution, in the step (2), the temperature of the heating and sealing reaction is 55-70° C., and the time is 4-6 h.

As a preference of the above technical solution, in the step (3), the freezing temperature of the freeze-thaw cycle treatment is -15--20°C, the freezing time is 15-18h, the melting temperature is 25-30°C, and the thawing temperature is 25-30°C. The time is 4-6h.

The present invention also provides the application method of any one of the transient hydrogel-modified composite gel separation membranes in dye sewage, which is characterized by comprising the following steps:

(1) after adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, stand at room temperature, and filter to obtain a sol-modified composite gel separation membrane for removing dyes;

(2) subjecting the dye-removed sol-modified composite gel separation membrane prepared in step (1) to a vortex oscillator to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

As a preference of the above technical solution, the transient hydrogel-modified composite gel separation membrane contains mechanically reinforced hydrogel and transient hydrogel, and the transient hydrogel will transform when standing at room temperature As a sol, the sol is transformed from a sol to a transient hydrogel by applying shear force and metal coordination through a vortex shaker.

As a preference of the above technical solution, the regenerated transient hydrogel-modified composite gel separation membrane obtained in the step (2) is cyclically applied to the step (1).

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

(1) The transient hydrogel-modified composite gel separation membrane prepared by the present invention contains mechanically enhanced hydrogel and transient hydrogel, wherein the mechanically enhanced hydrogel is made of polyethylene glycol and polymethacrylic acid. The composite gel separation membrane contains carbon nanotubes, and the composite gel separation membrane is freeze-thawed to remove polyethylene glycol in the composite gel, which is rich in porosity, which is beneficial to the placement of the transient hydrogel. Polyethylene glycol remains in the pores, therefore, the transient hydrogel and the mechanically enhanced hydrogel are uniformly dispersed. In addition, the transient hydrogel prepared by the present invention is based on the coordination between metal copper and ethylene glycol. As a link, the transient hydrogel will transform into a sol upon standing at room temperature, and the sol will transform from a sol to a transient hydrogel by applying shear force and metal coordination through a vortex oscillator, so the adsorbed The dye is released to realize the reuse of the dye separation membrane.

(2) The transient hydrogel-modified composite gel separation membrane prepared by the present invention contains a two-dimensional plane carrier, preferably a fabric, a nanofiber membrane or a polymer membrane, which improves the convenience of using the composite gel separation membrane. , reducing the cost of reuse.

Detailed ways

The present invention will be described in detail below with reference to specific embodiments. The exemplary embodiments and descriptions of the present invention are used to explain the present invention, but are not intended to limit the present invention.

Example 1:

(1) adding copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stirring to dissolve, according to the mass ratio of copper nitrate and carbon nanotubes to be 2:1, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content is 75%.

(2) Add methacrylic acid monomer (produced by Tianjin Hedong District Hongyan Reagent Factory) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.3:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes to be 1:0.1, add copper-loaded carbon nanotube solution, continue to stir evenly, add 1.5% of the system mass ammonium persulfate to induce Reagent (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully impregnated the fabric, passed nitrogen, heated and sealed at 55°C for 4 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -15 °C for 15 h, then thawed at 25 °C for 4 h, and subjected to three freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it is allowed to stand at room temperature for 12 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 800 r/min for 2 h to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

Example 2:

(1) adding copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stirring to dissolve, according to the mass ratio of copper nitrate and carbon nanotubes to be 3:1, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content is 85%.

(2) Add methacrylic acid monomer (produced by Hongyan Reagent Factory, Hedong District, Tianjin) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.4:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes is 1:0.2, add copper-loaded carbon nanotube solution, continue to stir evenly, add ammonium persulfate accounting for 1.5% of the system mass to induce (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully immersed the nanofiber membrane, passed nitrogen gas, heated and sealed at 70°C for 6 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -20 °C for 18 h, then thawed at 30 °C for 6 h, and subjected to 5 freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it was allowed to stand at room temperature for 24 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The sol-modified composite gel separation membrane with the dye removed was treated with a vortex shaker at a stirring rate of 1500 r/min for 4 h to obtain a composite gel separation membrane modified by regenerated transient hydrogels.

Example 3:

(1) Add copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stir until dissolved, and be 2.5:1 according to the mass ratio of copper nitrate and carbon nanotubes, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content of 78%.

(2) Add methacrylic acid monomer (produced by Tianjin Hedong District Hongyan Reagent Factory) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.35:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes is 1:0.3, add copper-loaded carbon nanotube solution, continue to stir evenly, add ammonium persulfate accounting for 1.5% of the system mass to initiate Reagent (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully immersed the polymer membrane in it, introduced nitrogen gas, heated and sealed at 60°C for 5 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -17 °C for 16 h, then thawed at 28 °C for 5 h, and subjected to four freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it was allowed to stand at room temperature for 16 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 1200 r/min for 2.5 hours to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

Example 4:

(1) adding copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stirring to dissolve, according to the mass ratio of copper nitrate and carbon nanotubes to be 2:1, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content of 78%.

(2) Add methacrylic acid monomer (produced by Tianjin Hedong District Hongyan Reagent Factory) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.38:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes is 1:0.2, add copper-loaded carbon nanotube solution, continue to stir evenly, add ammonium persulfate accounting for 1.5% of the system mass to induce Reagent (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully immersed the fabric in it, introduced nitrogen, heated and sealed at 65°C for 5.5 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -18 °C for 17 h, then thawed at 29 °C for 5.5 h, and subjected to four freeze-thaw cycles to obtain a transient hydrogel-modified composite gel. separation membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it was allowed to stand at room temperature for 20 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 1200 r/min for 3.5 hours to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

Example 5:

(1) adding copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stirring to dissolve, according to the mass ratio of copper nitrate and carbon nanotubes to be 2:1, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content is 85%.

(2) Add methacrylic acid monomer (produced by Tianjin Hedong District Hongyan Reagent Factory) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.3:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes is 1:0.3, add copper-loaded carbon nanotube solution, continue to stir evenly, add ammonium persulfate accounting for 1.5% of the system mass to initiate Reagent (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully immersed the nanofiber membrane in it, introduced nitrogen, heated and sealed at 70°C for 4 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -20 °C for 15 h, then thawed at 30 °C for 4 h, and subjected to 5 freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it is allowed to stand at room temperature for 12 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 1500 r/min for 2 h to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

Example 6:

(1) adding copper nitrate (produced by Sinopharm Chemical Reagent Co., Ltd.) into ethylene glycol (produced by Sinopharm Chemical Reagent Co., Ltd.), stirring to dissolve, according to the mass ratio of copper nitrate and carbon nanotubes to be 3:1, Add dropwise a solution of carbon nanotubes (3 μm in length, 6-8 nm in outer diameter, produced by Nanjing Xianfeng Nanomaterials Technology Co., Ltd.) to obtain a copper-loaded carbon nanotube solution, wherein the copper-loaded carbon nanotube solution is ethylene glycol The content is 75%.

(2) Add methacrylic acid monomer (produced by Hongyan Reagent Factory, Hedong District, Tianjin) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.4:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and copper-loaded carbon nanotubes to be 1:0.1, add copper-loaded carbon nanotube solution, continue to stir evenly, add 1.5% of the system mass ammonium persulfate to induce Reagent (produced by Hongyan Reagent Factory, Hedong District, Tianjin), fully impregnated the fabric, introduced nitrogen, heated and sealed at 55°C for 6 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -15 °C for 18 h, then thawed at 25 °C for 6 h, and subjected to three freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it was allowed to stand at room temperature for 24 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 800 r/min for 4 h to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

Comparative Example 1:

(1) Add methacrylic acid monomer (produced by Tianjin Hedong District Hongyan Reagent Factory) and polyethylene glycol (PEG400, chemically pure, produced by Sinopharm Chemical Reagent Co., Ltd.) with a mass ratio of 0.4:1 into deionized water , stir evenly, according to the mass ratio of methacrylic acid monomer and carbon nanotubes to be 1:0.1, add carbon nanotube solution, continue to stir evenly, add ammonium persulfate initiator (Hedong District, Tianjin City) that accounts for 1.5% of the mass of the system Hongyan Reagent Factory), fully immersed the fabric in it, introduced nitrogen, heated and sealed at 55°C for 6 hours, and took it out to obtain a copper-coordinated composite gel separation membrane.

(3) The copper-coordinated composite gel separation membrane was frozen at -15 °C for 18 h, then thawed at 25 °C for 6 h, and subjected to three freeze-thaw cycles to obtain a transient hydrogel-modified composite gel separation membrane. membrane.

(4) After adsorbing the dye wastewater by the transient hydrogel-modified composite gel separation membrane, it was allowed to stand at room temperature for 24 hours, and filtered to obtain a sol-modified composite gel separation membrane with dye removal.

(5) The dye-removed sol-modified composite gel separation membrane was treated with a vortex shaker at a stirring rate of 800 r/min for 4 h to obtain a regenerated transient hydrogel-modified composite gel separation membrane.

After testing, the results of the mechanical properties and swelling degree of the transient hydrogel-modified composite gel separation membranes prepared in Examples 1-6 and Comparative Example 1 are as follows:

After testing, the results of the dye residue rate and swelling degree of the regenerated transient hydrogel-modified composite gel separation membranes prepared in Examples 1-6 after repeated use for 10 times are as follows:

It can be seen from the above table that the transient hydrogel-modified composite gel separation membrane prepared by the present invention has good mechanical properties and adsorption properties, has regeneration performance, can be reused, and has low dye residue rate.

The above-mentioned embodiments merely illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed in the present invention should still be covered by the claims of the present invention.

Claims (10)

1. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel, it is characterised in that: the following steps are included:

(1) copper nitrate is added in ethylene glycol, stirring is added dropwise carbon nano-tube solution, obtains the carbon nanometer of supported copper to dissolving Pipe solution；

(2) methacrylic acid monomer and polyethylene glycol are added in deionized water, are stirred evenly, the negative of step (1) preparation is added Copper-loaded carbon nano-tube solution continues to stir evenly, and initiator is added, two-dimensional surface carrier is sufficiently impregnated wherein, to be passed through nitrogen Gas, heating sealing reaction, takes out, obtains the plural gel seperation film of cupric coordination；

(3) the plural gel seperation film of the cupric coordination of step (2) preparation is handled through Frozen-thawed cycled, it is modified obtains transient state hydrogel Plural gel seperation film.

2. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (1), the mass ratio of copper nitrate and carbon nanotube is 2-3:1.

3. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (1), the volume content of ethylene glycol is 75-85% in the carbon nano-tube solution of supported copper.

4. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (2), the mass ratio of methacrylic acid monomer and polyethylene glycol is 0.3-0.4:1.

5. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (2), two-dimensional surface carrier is fabric, nano fibrous membrane or polymer film.

6. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (2), the temperature of heating sealing reaction is 55-70 DEG C, time 4-6h.

7. a kind of preparation method of the modified plural gel seperation film of transient state hydrogel according to claim 1, feature Be: in the step (3), the temperature of the freezing of Frozen-thawed cycled processing is -15~-20 DEG C, and the time of freezing is 15-18h, is melted The temperature of change is 25-30 DEG C, and the time of thawing is 4-6h.

8. modified plural gel seperation film the answering in dye wastewater of any transient state hydrogel described in claim 1-7 With method, it is characterised in that: the following steps are included:

(1) it by after the modified plural gel seperation film absorption waste water from dyestuff of transient state hydrogel, stands at room temperature, filters, gone Except the sol-gel modified plural gel seperation film of dyestuff；

(2) the sol-gel modified plural gel seperation film of the removal dyestuff of step (1) preparation is handled through turbula shaker, is obtained Regenerate the modified plural gel seperation film of transient state hydrogel.

9. a kind of application of the modified plural gel seperation film of transient state hydrogel according to claim 8 in dye wastewater Method, which is characterized in that contain mechanical enhancing hydrogel and transient state in the modified plural gel seperation film of the transient state hydrogel Hydrogel, the transient state hydrogel is stood at room temperature can be changed into colloidal sol, and the colloidal sol is applied by turbula shaker to be sheared Power and metal coordination make to be changed into transient state hydrogel from colloidal sol.

10. a kind of modified plural gel seperation film the answering in dye wastewater of transient state hydrogel according to claim 8 With method, which is characterized in that the modified plural gel seperation film cycle applications of the regeneration transient state hydrogel that the step (2) obtains To step (1).