A method for preparing a metal-polymer hydrogen separation membrane with a sandwiched sandwich structure and applications thereof

Abstract

The application discloses a preparation method and application of a metal-polymer hydrogen separation membrane with a sandwiched sandwich structure, relates to the technical field of hydrogen separation membrane preparation, and specifically comprises the following steps: S1, preparing a sulfonated polyether ether ketone of a pure proton conductor and mixing the sulfonated polyether ether ketone with polybenzimidazole; S2, preparing a casting solution; S3, preparing a pure proton conductive layer; S4, preparing a dense film; S5, preparing a metal-polymer dense layer loaded with a Pt / C catalyst; S6, preparing a composite membrane with a sandwiched sandwich structure; S7, preparing Cu-Zn-Al2O3 and Ni-CeO2 catalysts; and S8, preparing the metal-polymer hydrogen separation membrane with a sandwiched sandwich structure. The metal-polymer hydrogen separation membrane has 100% selectivity to H2.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of hydrogen separation membrane preparation, in particular to a preparation method and application of a metal-polymer hydrogen separation membrane with a sandwich structure. BACKGROUND

[0002] At present, hydrogen is mainly prepared by reforming fossil fuels, but the separation of impurity gas is difficult. Therefore, under the operation condition, a suitable hydrogen separation membrane is selected or developed, which is one of the key problems of membrane separation hydrogen production.

[0003] The coupling membrane reactor process can eliminate CO in the mixed gas, additionally produce more H2, and through CO2 methanation, H2 can be effectively utilized while CO2 is consumed, so that energy saving and emission reduction are achieved. SUMMARY

[0004] The application provides a preparation method and application of a metal-polymer hydrogen separation membrane with a sandwich structure.

[0005] In order to achieve the above purpose, the technical scheme adopted by the application is as follows:

[0006] The application provides a preparation method of a metal-polymer hydrogen separation membrane with a sandwich structure, which specifically comprises the following steps:

[0007] S1: a pure proton conductor sulfonated polyether ether ketone (SPEEK) is prepared, mixed with polybenzimidazole (OPBI), and mixed powder is obtained;

[0008] S2: the mixed powder is dissolved in dimethyl sulfoxide (DMSO), and the casting solution is prepared by stirring and mixing;

[0009] S3: the casting solution is defoamed by using ultrasonic technology (90W, 30min), and then the casting solution is prepared into a pure proton conductive layer by coating technology and a drying method;

[0010] S4: the pure proton conductive layer is respectively soaked in amino-trimethylene phosphonic acid (ATMP) and phosphoric acid (PA), and a dense film is obtained;

[0011] S5: Pt / C catalyst is uniformly loaded on both sides of the dense film by using an ion sputtering instrument, and a metal-polymer dense layer loaded with Pt / C catalyst is obtained;

[0012] S6: the metal-polymer dense layer loaded with Pt / C catalyst is tightly wrapped in the middle by using a foam nickel layer, and a composite membrane with a sandwich structure is formed;

[0013] S7: Cu-Zn-Al2O3 and Ni-CeO2 catalysts are prepared;

[0014] S8: Cu-Zn-Al2O3 and Ni-CeO2 catalysts are loaded on the foam nickel layers on both sides of the composite membrane by ion sputtering method, to obtain a metal-polymer hydrogen separation membrane with a sandwich structure.

[0015] Further, in the step S1, the mass ratio of the sulfonated polyether ether ketone to the polybenzimidazole is 7:3; the preparation method of the sulfonated polyether ether ketone is specifically as follows: polyether ether ketone powder (PEEK) is dissolved in sulfuric acid, and stirred at 300 r / min at room temperature for 24 h, and then heated and stirred at 50℃ for 40 min; after the reaction is completed, the solution is slowly poured into deionized water while stirring, to obtain a white fibrous substance, which is continuously washed with a large amount of deionized water until the pH approaches neutral; the sulfonated polyether ether ketone powder is obtained by suction filtration and drying at 110℃ for 12 h; the solid-liquid ratio of the polyether ether ketone powder to sulfuric acid is 5 g:100 mL; and the volume ratio of sulfuric acid to deionized water is 1:10.

[0016] Further, in the step S2, the preparation of the casting solution is specifically as follows: the mixed powder of step S1 is dissolved in dimethyl sulfoxide, heated and stirred at 100℃ in an oil bath for 24 h at 300 r / min, and after cooling to room temperature, ultrasonic treatment is performed at 90 W for 30 min, to obtain the casting solution; the solid-liquid ratio of the mixed powder to dimethyl sulfoxide is 1 g:20 mL.

[0017] Further, in the step S3, the specific method for preparing the pure proton conductive layer from the casting solution by coating technology and drying method is as follows:

[0018] S31: A smooth and clean aluminum foil paper is laid on a film coating machine, and a vacuum button is turned on to make the aluminum foil paper flatly adsorbed on the surface of the film coating machine;

[0019] S32: The defoamed casting solution is uniformly dispersed on the aluminum foil paper;

[0020] S33: The thickness of the film is set to 100 μm, the coating machine parameters are adjusted, the film scraping speed is 2 mm / s, and automatic film scraping is performed;

[0021] S34: The wet film is placed in a drying box, dried at 40℃ for 3 h, and vacuum dried at 80℃ for 12 h, to obtain the pure proton conductive layer.

[0022] Further, in the step S4, the preparation method of the dense film is specifically as follows: the pure proton conductive layer is soaked in amino-trimethylene phosphonic acid at 100℃ for 24 h, dried at 80℃ for 12 h, soaked in phosphoric acid at 60℃ for 72 h, and then vacuum dried at 80℃ for 24 h.

[0023] Further, in the step S5, the specific method for uniformly loading the Pt / C catalyst on both sides of the dense film using an ion sputtering instrument is as follows: placing the cut dense film (1.1-1.2 cm in diameter) on the operating table of the ion sputtering instrument, spraying platinum, and loading the Pt / C catalyst on both surfaces, thereby obtaining a metal-polymer dense layer loaded with the Pt / C catalyst; the sputtering time is 2 min, the current is 20 mA, and the vacuum degree is 3 Pa.

[0024] Further, in the step S6, the preparation method of the composite film with a sandwich structure is as follows: hot-pressing the metal-polymer dense layer loaded with the Pt / C catalyst and the foam nickel on both sides in a three-in-one manner, and the specific hot-pressing steps are as follows: pre-pressing the foam nickel for 2-3 min at room temperature by using a tablet press, so that the surface is smooth; then placing the pre-pressed foam nickel on both sides of the metal-polymer dense layer loaded with the Pt / C catalyst, cutting the foam nickel into a circle with a diameter of 1.5 cm, cutting the dense layer into a circle with a diameter of 1.2 cm, and using an automatic tablet press to co-press the three layers, the pressure is 3-5 MP, the temperature of the upper and lower plates is 110°C, and the hot-pressing time is 150 s, thereby obtaining the composite film with a sandwich structure.

[0025] Further, in the step S7,

[0026] The preparation method of the Cu-Zn-Al2O3 is as follows: using a coprecipitation method, mixing 0.25 mol / L of Cu(NO3)2·3H2O, 0.2 mol / L of Zn(NO3)2·6H2O, and 0.05 mol / L of Al(NO3)3·9H2O aqueous solutions to obtain a mixed aqueous solution; adding 1M of Na2CO3 solution dropwise to the mixed aqueous solution to obtain a mixed reagent; dissolving the mixed reagent in deionized water, adding Na2CO3 solution to adjust the pH to 7, then aging the solution for 0.5 h, filtering, washing the precipitate with 60°C hot deionized water, drying at 110°C for 24 h, and then calcining at 723K for 3 h in a nitrogen and oxygen flowing gas mixture with a volume ratio of 4:1, thereby obtaining the Cu-Zn-Al2O3.

[0027] The volume ratio of the Cu(NO3)2·3H2O, Zn(NO3)2·6H2O, Al(NO3)3·9H2O aqueous solution, Na2CO3 solution, and deionized water is 2:2:2:3:250;

[0028] The preparation method of the Ni-CeO2 is as follows: using a wet impregnation method, the CeO2 is dried in an oven at 120 DEG C overnight to remove excess water to obtain a CeO2 powder; a nickel nitrate powder is weighed and dissolved in deionized water to form a nickel nitrate solution, the CeO2 powder is slowly added under continuous stirring, after a uniform suspension is formed, the temperature is slowly increased to 60 DEG C, and the heating and stirring are continued until the liquid is completely volatilized, the catalyst powder is collected, transferred to a drying oven at 120 DEG C for 12 hours, and after being fully ground, the temperature is increased to 300 DEG C at a temperature increasing rate of 1 DEG C / min for calcination for 2 hours, and then the temperature is increased to 450 DEG C at a temperature increasing rate of 2 DEG C / min for roasting for 2 hours, and the Ni-CeO2 is obtained;

[0029] The solid-liquid ratio of the nickel nitrate powder, deionized water and CeO2 powder is 1.32g:16mL:2.4g.

[0030] Further, the specific operation of the step S8 is as follows: the composite film is placed on an operating table of an ion sputtering instrument, the catalyst is loaded, the Cu-Zn-Al2O3 and the Ni-CeO2 catalysts are respectively loaded on the foam nickel layers on the two sides of the composite film, and the sandwiched three-layer structure metal-polymer hydrogen separation film is obtained.

[0031] The sputtering time is 2min, the current is 20mA, and the vacuum degree is 3Pa.

[0032] The application also provides an application of the sandwiched three-layer structure metal-polymer hydrogen separation film prepared by the preparation method.

[0033] The sandwiched three-layer structure metal-polymer hydrogen separation film provided by the application comprises a foam nickel and a metal-polymer dense layer loaded with a Pt / C catalyst, the dense layer is formed by mixing two organic matters, the sulfonic acid groups in the SPEEK and the amino groups in the OPBI can easily form a continuous and dense proton transfer network through acid-base interaction, and the foam nickel is a material for conducting protons.

[0034] Compared with the prior art, the sandwiched three-layer structure metal-polymer hydrogen separation film has the following beneficial effects:

[0035] In the present application, by combining the separation mechanism of "hydrogen pump" and ceramic proton-electron mixed conductive film, a metal-polymer hydrogen separation membrane with 100% selectivity for H2 is provided. First, the metal-polymer dense composite film prepared in the present application simultaneously opens the transmission channels of protons and electrons in the film, compared with the traditional hydrogen separation organic film, the hydrogen separation selectivity can be theoretically improved to 100%, and high-purity hydrogen (more than 99.999%) can be obtained after separation. Secondly, the high electron conduction capacity of the foamed nickel coating can well replace the external circuit. Finally, by reasonably constructing the membrane reactor, H2 can be efficiently separated while CO2 can be consumed to prepare chemicals, achieving the effect of double carbon emission reduction. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is the principle diagram of the metal-polymer hydrogen separation membrane with a sandwiched sandwich structure of the present application separating H2;

[0037] Figure 2 is the device diagram of the metal-polymer hydrogen separation membrane with a sandwiched sandwich structure of the present application separating H2 coupled with a membrane reactor;

[0038] REFERENCE NUMERALS: Figure 2 In the figure: 1 is a gas chromatograph, 2 is a self-made reactor, 3 is a heating furnace, 4 is a temperature controller, 5 is an air pipe, 6 is a flow controller, 7 is a metal-polymer hydrogen separation membrane, and 8 is a water vapor injection pump. DETAILED DESCRIPTION

[0039] In order to make the purpose and advantages of the present application clearer and more apparent, the present application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0040] The instruments, reagents, materials, etc. involved in the following examples, if not specifically stated, are conventional instruments, reagents, materials, etc. already existing in the prior art, which can be obtained through regular commercial channels. The experimental methods, detection methods, etc. involved in the following examples, if not specifically stated, are conventional experimental methods, detection methods, etc. already existing in the prior art.

[0041] Example 1

[0042] The present embodiment provides a preparation method of a metal-polymer hydrogen separation membrane with a sandwiched sandwich structure, which specifically comprises the following steps:

[0043] S1: prepare a pure proton conductor sulfonated polyether ether ketone (SPEEK), and mix it with polybenzimidazole (OPBI) at a mass ratio of 7:3 to obtain a mixed powder;

[0044] The preparation method of the sulfonated polyether ether ketone is specifically as follows: 5 g of polyether ether ketone powder (PEEK) is dissolved in 100 mL of sulfuric acid, and stirred at 300 r / min at room temperature for 24 h, and then heated to 50 DEG C and stirred for 40 min; after the reaction is completed, the solution is slowly poured into 1000 mL of deionized water while stirring, to obtain a white fibrous material, which is continuously washed with a large amount of deionized water until the pH approaches neutral; the material is filtered and dried at 110 DEG C for 12 h to obtain sulfonated polyether ether ketone powder;

[0045] S2: 1 g of the mixed powder is weighed, and 20 mL of DMSO is weighed and poured into the beaker containing the mixed powder, and the beaker is placed in an oil bath at 100 DEG C and heated and stirred at 300 r / min for 24 h; after cooling to room temperature, 90 W ultrasonic treatment is performed for 30 min to obtain a casting solution;

[0046] S3: the casting solution is defoamed by ultrasonic treatment (90 W ultrasonic treatment for 30 min), and then the casting solution is prepared into a pure proton conductive layer by coating technology and drying method, and the specific method is as follows:

[0047] S31: a smooth and clean aluminum foil paper is laid on the film coating machine, and the vacuum button is turned on to make the aluminum foil paper flatly adsorbed on the surface of the film coating machine;

[0048] S32: the defoamed casting solution is uniformly dispersed on the aluminum foil paper;

[0049] S33: the thickness of the film is set to 100 mu m, the coating machine parameters are adjusted, and automatic film scraping (scraping speed is 2 mm / s) is performed until the film surface is smooth and flat;

[0050] S34: the wet film is placed in a drying box (40 DEG C drying for 3 h, 80 DEG C vacuum drying for 12 h) to obtain a pure proton conductive layer;

[0051] S4: the pure proton conductive layer is soaked in amino-trimethylene phosphonic acid (ATMP) at 100 DEG C for 24 h, dried at 80 DEG C for 12 h, soaked in phosphoric acid (PA) at 60 DEG C for 72 h, and then washed with deionized water, and the film is placed in a vacuum drying box and dried at 80 DEG C for 24 h to obtain a dense film;

[0052] S5: the cut dense film (diameter 1.1-1.2 cm) is placed on the operation table of the ion sputtering instrument, platinum is sprayed, the sputtering time is 2 min, the current is 20 mA, and the vacuum degree is 3 Pa, and Pt / C catalyst is loaded on both surfaces to obtain a metal-polymer dense layer loaded with Pt / C catalyst;

[0053] S6: Pre-pressing the nickel foam for 2-3 min at room temperature by a tablet press with a pressure of 3-5 MPa to make its surface smooth and flat; then placing the pre-pressed nickel foam on both sides of the metal-polymer dense layer loaded with Pt / C catalyst, cutting the nickel foam into a circle with a diameter of 1.5 cm and the dense layer into a circle with a diameter of 1.2 cm, and using an automatic tablet press to co-press the three layers with a pressure of 3-5 MPa, an upper and lower plate temperature of 110°C, and a hot-pressing time of 150 s to complete the construction of the entire composite membrane electronic channel, thereby obtaining a sandwich-structured composite membrane;

[0054] S7: Preparing Cu-Zn-Al2O3 and Ni-CeO2 catalysts;

[0055] The preparation method of Cu-Zn-Al2O3 is as follows: 2 mL of an aqueous solution of 0.25 mol / L Cu(NO3)2·3H2O, 0.2 mol / L Zn(NO3)2·6H2O and 0.05 mol / L Al(NO3)3·9H2O is mixed to obtain a mixed aqueous solution; 3 mL of 1M Na2CO3 solution is added dropwise to the mixed aqueous solution to obtain a mixed reagent; the mixed reagent is dissolved in 250 mL of deionized water, and the pH is adjusted to 7 by adding a Na2CO3 solution at a rate of 3 mL·min -1 -1 to obtain a solution; the solution is aged for 0.5 h, filtered, and the precipitate is washed with hot deionized water at 60°C; after drying at 110°C for 24 h, the product is calcined at 723 K for 3 h in a nitrogen and oxygen flowing gas mixture (N2:O2=4:1) to obtain Cu-Zn-Al2O3;

[0056] The preparation method of Ni-CeO2 is as follows: using a wet impregnation method, CeO2 is dried in an oven at 120°C overnight to remove excess water to obtain CeO2 powder; 1.32 g of nickel nitrate powder (Ni(NO3)2·6H2O) is weighed and dissolved in 16 mL of deionized water to form a nickel nitrate solution; 2.4 g of CeO2 powder is slowly added under continuous stirring, and after a uniform suspension is formed, the solution is slowly heated to 60°C; continue heating and stirring until the liquid is completely volatilized; collect the catalyst powder and transfer it to a drying oven at 120°C for 12 h; after grinding, heat it to 300°C at a rate of 1°C / min and calcine for 2 h; then heat it to 450°C at a rate of 2°C / min and calcine for 2 h to obtain Ni-CeO2;

[0057] S8: Put the composite membrane on the operating table of the ion sputtering instrument, load the catalyst, sputtering time is 2 min, current is 20 mA, vacuum degree is 3 Pa, Cu-Zn-Al2O3 and Ni-CeO2 catalysts (used for catalyzing water gas shift and CO2 methanation reaction respectively) are loaded on the foam nickel layers on both sides of the composite membrane respectively, a metal-polymer hydrogen separation membrane with sandwich structure is obtained, the separation mechanism of the hydrogen separation membrane and the process principle diagram of the coupled membrane reactor are shown in the accompanying Figure 1 .

[0058] The principle of metal-polymer composite membrane separating hydrogen and the process of coupled membrane reactor is as follows:

[0059] The mixed gas atmosphere generated by water gas shift (CO+H2O→CO2+H2) reaction is introduced into the side of the composite membrane loaded with Cu-Zn-Al2O3 catalyst, CO2 and H2 are generated under the action of the catalyst, H + and e - are generated on the feed side under the action of Pt / C catalyst on both sides of the metal-polymer hydrogen separation membrane, then the concentration difference existing on both sides of the metal-polymer hydrogen separation membrane is used as driving force, protons jump through the hydrogen bonds formed by the amino groups in OPBI and the sulfonic acid groups in SPEEK, and electrons are conducted through the foam nickel phase, H + and e - are recombined into H2 molecules under the action of Pt catalytic layer on the sweep side of the membrane, H2 separation is realized. The permeated H2 reacts with CO2 under the action of Ni-CeO2 to generate CH4 (CO2+4H2→CH4+2H2O).

[0060] The device diagram of metal-polymer hydrogen separation membrane separating H2 is shown in the accompanying Figure 2 , the device includes a gas chromatograph 1, a laboratory-made reactor 2, a heating furnace 3, a temperature controller 4, a gas pipeline 5, a flow controller 6, a metal-polymer hydrogen separation membrane 7, and a water vapor injection pump 8.

[0061] For the feed coupled water gas shift reaction:

[0062] Experimental Example 1

[0063] On the feed side of the membrane, before the reaction starts, water is injected to generate water vapor, then a mixed gas composed of CO and N2 is introduced and uniformly mixed with the water vapor, and the other side is swept with pure Ar. The temperature of the heating furnace is controlled at 120°C.

[0064] Experimental Example 2

[0065] Using the metal-polymer hydrogen separation membrane prepared in Example 1, the reaction temperature was controlled by a horizontal tube furnace, and the performance of the metal-polymer hydrogen separation membrane prepared under the conditions identical to those in Experimental Example 1 except that the reaction temperature was 140°C was tested.

[0066] Experimental Example 3

[0067] Using the metal-polymer hydrogen separation membrane prepared in Example 1, the performance of the metal-polymer hydrogen separation membrane prepared under the conditions identical to those in Experimental Example 1 except that the reaction temperature was 160°C was tested.

[0068] Before the start of the membrane reactor test, the basic operating conditions such as temperature and space velocity were evaluated using a fixed bed, so as to facilitate the operation of the membrane reactor after the optimum conditions were obtained, as shown in Tables 1-4.

[0069] Table 1 Conversion rate (%) of CO with respect to temperature

[0070]

[0071] Table 2 Conversion rate (%) of CO with respect to space velocity at 160°C

[0072]

[0073] Table 3 Conversion rate of CO with respect to S / C (H2O / CO) at 160°C, space velocity 2500 h -1

[0074]

[0075] Table 4 Conversion rate with respect to S / C (H2O / CO) at 160°C, space velocity 2500 h -1

[0076]

[0077] For the permeation measurement coupled with the carbon dioxide methanation reaction:

[0078] Experimental Example 4

[0079] A mixed gas composed of H2, CO2 and N2 in a molar ratio of 16:4:5 was introduced, and the reaction was carried out at a space velocity of 56,000 h -1

[0080] Experimental Example 5

[0081] ​​​The metal-polymer hydrogen separation membrane prepared in Example 1 was used to perform performance test under the condition that the reaction temperature was controlled by a horizontal tube furnace and the reaction temperature was 120℃, which was consistent with the condition in Experimental Example 1.

[0082] Experimental Example 6

[0083] The metal-polymer hydrogen separation membrane prepared in Example 1 was used to perform performance test under the condition that the reaction temperature was controlled by a horizontal tube furnace and the reaction temperature was 140℃, which was consistent with the condition in Experimental Example 1.

[0084] Experimental Example 7

[0085] The metal-polymer hydrogen separation membrane prepared in Example 1 was used to perform performance test under the condition that the reaction temperature was controlled by a horizontal tube furnace and the reaction temperature was 160℃, which was consistent with the condition in Experimental Example 1.

[0086] Experimental Example 8

[0087] The metal-polymer hydrogen separation membrane prepared in Example 1 was used to perform performance test under the condition that the reaction temperature was controlled by a horizontal tube furnace and the reaction temperature was 180℃, which was consistent with the condition in Experimental Example 1.

[0088] Table 5 Conversion rate of CO2 with temperature change (%)

[0089]

[0090] The metal-polymer hydrogen separation membrane prepared in the example can be used to separate high-purity H2. As can be seen from Table 1, the metal-polymer two-phase dense membrane has a good H2 permeation flux, thereby proving that protons can be conducted through the hydrogen bond generated by the sulfonic acid group and the amino group on the OPBI, and electrons are conducted through the foamed nickel. As can be seen from Tables 1-5, by constructing a membrane reactor between the feed and the permeation, high-efficiency hydrogen separation can be achieved, and hydrogen utilization and CO2 consumption can be achieved.

[0091] In summary, the metal-polymer hydrogen separation membrane with a sandwich structure of the present application can theoretically increase the selectivity of hydrogen separation to 100%, and can directly obtain high-purity hydrogen meeting the standard of more than 99.999% purity after separation, and the entire separation link does not need to rely on an external circuit to provide voltage driving. At the same time, two catalytic reactions can be coupled on both sides of the membrane, and the three processes of “H2 generation-H2 separation-H2 conversion and utilization” can be combined into one.

[0092] The above merely describes preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a metal-polymer hydrogen separation membrane in a sandwiched sandwich structure, characterized by: Specifically comprising the following steps: S1: preparing a sulfonated polyether ether ketone of pure proton conductor, mixing with polybenzimidazole to obtain a mixed powder; S2: dissolving the mixed powder in dimethyl sulfoxide, stirring and mixing into a casting solution; S3: defoaming the casting solution by ultrasonic technology, and then preparing the casting solution into a pure proton conductive layer by coating technology and drying method; S4: immersing the pure proton conductive layer in amino-trimethylene phosphonic acid and phosphoric acid respectively to obtain a dense film; S5: uniformly loading Pt / C catalyst on both sides of the dense film by using an ion sputtering instrument to obtain a metal-polymer dense layer loaded with Pt / C catalyst; S6: tightly wrapping the metal-polymer dense layer loaded with Pt / C catalyst in the middle using a foam nickel layer to form a composite membrane with a sandwich structure; S7: preparing Cu-Zn-Al2O3 and Ni-CeO2 catalysts; S8: loading the Cu-Zn-Al2O3 and Ni-CeO2 catalysts on the foam nickel layers on both sides of the composite membrane by ion sputtering method to obtain a metal-polymer hydrogen separation membrane with a sandwich structure.

2. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S1, the mass ratio of the sulfonated polyether ether ketone to the polybenzimidazole is 7:3; the preparation method of the sulfonated polyether ether ketone is specifically as follows: dissolving polyether ether ketone powder in sulfuric acid, stirring at 300 r / min at room temperature for 24 h, and then stirring at 50℃ for 40 min; after the reaction is completed, slowly pouring the solution into deionized water while stirring to obtain a white fibrous material, and continuously washing with a large amount of deionized water until the pH approaches neutral; after filtration and drying at 110℃ for 12 h, the sulfonated polyether ether ketone powder is obtained; the solid-liquid ratio of the polyether ether ketone powder to sulfuric acid is 5 g:100 mL; and the volume ratio of sulfuric acid to deionized water is 1:

10.

3. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S2, the preparation of the casting solution is specifically as follows: dissolving the mixed powder of step S1 in dimethyl sulfoxide, heating and stirring at 100℃ in an oil bath for 24 h at 300 r / min, and then cooling to room temperature, and then ultrasonic treatment at 90 W for 30 min to obtain the casting solution; the solid-liquid ratio of the mixed powder to dimethyl sulfoxide is 1 g:20 mL.

4. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S3, the specific method for preparing the pure proton conductive layer from the casting solution by coating technology and drying method is as follows: S31: laying a smooth and clean aluminum foil paper on a film coating machine, and at the same time, turning on the vacuum button to make the aluminum foil paper flatly adsorbed on the surface of the film coating machine; S32: uniformly dispersing the defoamed casting solution on the aluminum foil paper; S33: setting the thickness of the film to 100 μm, adjusting the coating machine parameters, and automatically scraping the film at a speed of 2 mm / s; S34: placing the wet film into a drying box, drying at 40℃ for 3 h, and then vacuum drying at 80℃ for 12 h to obtain the pure proton conductive layer.

5. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S4, the preparation method of the dense film is specifically as follows: immersing the pure proton conductive layer in amino-trimethylene phosphonic acid at 100℃ for 24 h, drying at 80℃ for 12 h, then immersing in phosphoric acid at 60℃ for 72 h, and then vacuum drying at 80℃ for 24 h.

6. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S5, the specific method for uniformly loading the Pt / C catalyst on both sides of the dense film using an ion sputtering instrument is as follows: the cut dense film is placed on the operating table of the ion sputtering instrument, platinum is sprayed, and the Pt / C catalyst is loaded on both surfaces, thereby obtaining the metal-polymer dense layer loaded with the Pt / C catalyst; the sputtering time is 2 min, the current is 20 mA, and the vacuum degree is 3 Pa.

7. The method of claim 1, wherein the metal-polymer hydrogen separation membrane of the sandwiched structure is prepared by the steps of: (a) providing a porous polymer membrane; (b) providing a metal layer; (c) providing a polymer layer; (d) providing a metal layer; (e) providing a polymer layer; and (f) providing a metal layer. In the step S6, the preparation method of the composite film in the sandwich structure is as follows: the metal-polymer dense layer loaded with the Pt / C catalyst and the foam nickel on both sides are combined and hot-pressed, and the specific hot-pressing steps are as follows: the foam nickel is pre-pressed for 2-3 min at room temperature by a tablet press, and the pressure is 3-5 MPa, so that the surface is smooth; then the pre-pressed foam nickel is placed on both sides of the metal-polymer dense layer loaded with the Pt / C catalyst, the foam nickel is cut into a circle with a diameter of 1.5 cm, the dense layer is cut into a circle with a diameter of 1.2 cm, and the three layers are co-pressed by using an automatic tablet press, the pressure is 3-5 MPa, the temperature of the upper and lower plates is 110℃, and the hot-pressing time is 150 s, thereby obtaining the sandwich structure.

8. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: In the step S7, The preparation method of the Cu-Zn-Al2O3 is as follows: a coprecipitation method is used, 0.25 mol / L of Cu(NO3)2·3H2O, 0.2 mol / L of Zn(NO3)2·6H2O and 0.05 mol / L of Al(NO3)3·9H2O aqueous solution are mixed to obtain a mixed aqueous solution; 1M Na2CO3 solution is added dropwise to the mixed aqueous solution to obtain a mixed reagent; the mixed reagent is dissolved in deionized water, Na2CO3 solution is added to adjust the pH to 7, and then the solution is aged for 0.5 h, filtered, and the precipitate is washed with 60℃ hot deionized water, dried at 110℃ for 24 h, and then calcined in a nitrogen and oxygen flowing gas mixture with a volume ratio of 4:1 at 723K for 3 h, thereby obtaining the Cu-Zn-Al2O3; The volume ratio of the Cu(NO3)2·3H2O, Zn(NO3)2·6H2O, Al(NO3)3·9H2O aqueous solution, Na2CO3 solution and deionized water is 2:2:2:3:250; The preparation method of the Ni-CeO2 is as follows: a wet impregnation method is used, CeO2 is dried in a 120℃ oven overnight to remove excess water, thereby obtaining CeO2 powder; nickel nitrate powder is weighed and dissolved in deionized water to form a nickel nitrate solution, and the CeO2 powder is slowly added under continuous stirring, and after a uniform suspension is formed, the temperature is slowly increased to 60℃, and the heating and stirring are continued until the liquid is completely volatilized, the catalyst powder is collected, transferred to a drying oven for drying at 120℃ for 12 h, and after being ground, the temperature is increased to 300℃ at a rate of 1℃ / min and calcined for 2 h, and then the temperature is increased to 450℃ at a rate of 2℃ / min and calcined for 2 h, thereby obtaining the Ni-CeO2; The solid-liquid ratio of the nickel nitrate powder, deionized water and CeO2 powder is 1.32 g:16 mL:2.4 g.

9. The method for preparing a sandwich-structured metal-polymer hydrogen separation membrane according to claim 1, characterized in that: The specific operation of the step S8 is: placing the composite film on the operating table of the ion sputtering instrument, loading the catalysts, and loading Cu-Zn-Al2O3 and Ni-CeO2 catalysts on the foam nickel layers on the two sides of the composite film respectively, so as to obtain a metal-polymer hydrogen separation film with a sandwich structure; the sputtering time is 2 min, the current is 20 mA, and the vacuum degree is 3 Pa.

10. Use of a metal-polymer hydrogen separation membrane in a sandwiched structure prepared according to the method of any one of claims 1 to 9, characterized in that: The hydrogen separation film is used for H2 separation, and three processes of H2 generation, H2 separation and H2 conversion utilization are combined into one.

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