KR101715875B1 - Support Integrated Hydrogen Separation Membrane and Method for Manufacturing the Same - Google Patents

Abstract

The present invention relates to a hydrogen permeable membrane having improved hydrogen selectivity and hydrogen permeability at the same time by producing an integrated hydrogen separation membrane in which structural, compositional, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer are gradually and continuously changed Provided is a support-integrated hydrogen separation membrane having stable durability by forming an interface of a uniform solid solution having excellent adhesion and a method for producing the same.
Furthermore, the support-integrated hydrogen separation membrane according to the present invention has a simple, efficient, and highly reproducible production process with high production efficiency, and can be used not only in the field of hydrogen purification but also in the field of hydrogen separation (SERP) It can be widely applied to coal gasification combined cycle power generation (IGCC), carbon dioxide capture and storage (CCS), and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a support-integrated hydrogen separation membrane and a method for manufacturing the same,

The present invention relates to a support-integrated hydrogen separation membrane and a method for manufacturing the same. More particularly, the present invention relates to a method for producing a hydrogen permeable membrane and a method for producing a hydrogen permeable membrane by simultaneously and continuously changing the structural, combinatorial, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer And also has excellent durability in a long-term extreme commercialization atmosphere, and a method for producing the same.

Research on the use of natural gas, fossil fuels such as coal, and biomass as synthesis gas containing hydrocarbons by reforming and using it as an alternative energy due to lack of petroleum resources is going on. As such, hydrogen, a component mainly contained in syngas, is not generated when it is used as an energy source. It is easily transported to gas or liquid and can be energized in various forms such as high pressure gas, liquid hydrogen and metal hydride Provides advantages that can be achieved.

Accordingly, the hydrogen separation and purification process using hydrogen as an energy source has attracted attention, and the membrane separation method showing various advantages such as a simple process configuration, a high hydrogen recovery rate, a low installation cost and a small installation space is the most promising for high purity hydrogen production Technology. Among these membrane separation processes, palladium alloy hydrogen separation membranes, which are inorganic membrane catalyst technologies, are widely used because of their high permeation selectivity to hydrogen, excellent thermal, chemical and mechanical properties. This hydrogen separation membrane technology can be used not only for the production of high purity hydrogen but also for sorption enhanced reaction process (SERP), integrated gasification combined cycle (IGCC), carbon capture and storage Storage, and CCS), and offers various advantages.

Since the palladium alloy hydrogen separation membrane used in the conventional hydrogen production process such as hydrogen separation and purification has a high hydrogen selectivity due to the non-porous palladium alloy membrane, the palladium alloy membrane is coated on the porous support to improve the selective permeability of hydrogen Research is underway. However, in the case of a conventional manufacturing method in which a non-porous palladium alloy layer is coated to increase the selective permeability of hydrogen, the palladium alloy layer may not be formed densely depending on the pore state or surface roughness of the surface of the porous support, Defects were present, and high hydrogen selectivity could not be obtained. The manufacturing process by the conventional high temperature sputtering process (KR 10-1176585), copper reflow (US 7,875,152 B2) and Ag-up filling (KR 10-1271394) heat treatment etc. have dense microstructure, However, since the thickness of the palladium-coated alloy layer is as thick as a few microns and the interface between the support and the hydrogen separation layer is dense and hydrogen permeation is difficult to occur easily, there is a disadvantage in that hydrogen permeability But did not show any significant improvement in terms of In order to improve the hydrogen permeability, the conventional hydrogen permeable membranes having the maximum permeation composition and the open structure have improved hydrogen permeability and hydrogen permeability (KR 10-1459673). However, As the support metal components diffuse to the membrane surface, unstable high temperature durability and low reproducibility due to a series of complicated processes were exhibited. In addition, the porous support, the interface and the palladium alloy hydrogen separation layers formed independent structures, respectively, and ultimately exhibited separator characteristics in which hydrogen permeation permeability and durability were degraded.

Under such conventional technical background, there is a problem that not only the functionality of the hydrogen separation membrane for hydrogen separation and purification but also durability and reproducibility for commercialization are inevitably low. In order to efficiently apply hydrogen membrane technology to various industrial fields such as high purity hydrogen production, simultaneous reaction separation for hydrogen separation and purification, coal gasification combined cycle power generation, coal-use fuel cell power generation, and CO2 capture and storage, It is essential to have excellent hydrogen permeation selectivity and durability in a high temperature and high pressure commercial environment.

In order to simultaneously improve the hydrogen permeation selectivity and durability, it is necessary to reduce the separation layer thickness and to prevent the surface diffusion of the support metal components while maintaining the alloy composition of the palladium alloy film in which the hydrogen permeability is maximized along with the surface densification of the hydrogen separation layer . In addition, structural and chemical stability such as microstructure and interfacial adhesion of membranes must be maintained constantly while maintaining the above-mentioned functional characteristics under the conditions of commercialization of high temperature and high pressure for a long period of time. In addition, structural, functional, and functional properties of the porous support, interface, and hydrogen separation layers should be fabricated from monolithic membranes with improved durability. In order to apply hydrogen separation membranes having the above characteristics to commercialization, the detailed processes must be mutually compatible, and a series of pre-processes must be simple and excellent in reproducibility. In addition, It should be a manufacturing method.

1. KR 10-1459673 2. KR 10-1176585 3. US 7,875,154 B2 4. KR 10-0832302 5. KR 10-1136853 6. KR 10-1271394 7. US 7,255,726

1. Formation of defect-free Pd-Cu-Ni alloy membrane on a polished porous nickel support (PNS), S. K. Ryi, J. S. Park, S. H. Kim, D. W. Kim, K. I. Cho: J. Membr. Sci., 318 (2008) 346-354 2. The effect of Cu reflow on the Pd-Cu-Ni ternary alloy membrane fabrication for infinite hydrogen separation. Lee, JK Park, JW Moon, SK Lee, JS Park, 3036-3044 3. Pd-Ag membrane synthesis: The electroless and electro-plating conditions and their effect on the deposits morphology., R. Bhandari, Y. H. Ma: J. Membr. Sci., 334 (2009) 50-63 4. Palladium and Palladium alloy membranes for hydrogen separation and production: History, fabrication strategies, and current performance. Hatlevik, S. K. Grade, M. K. Kelling, P. M. Thoen, A. P. Davidson, J. D. Way: Sep. Purif. Technol., 73 (2010) 59-64 5. Development of Pd alloy hydrogen separation membranes with dense / porous hybrid structure for high hydrogen permselectivity. J. Y. Han, C. H. Kim, S. H. Kim, D. W. Kim: Advanced in Materials Science and Engineering, 438216 (2014) 6. Improvement in Long-term Stability of Pd Alloy Hydrogen Separation Membranes, C. H. Kim, J. H. Lee, S. T. Jo, D. W. Kim, J. Kor. Inst. Surf. Eng., 48 (2015) 11-22) 7. Inluence of substrate temperature and deposition rate on structure of thick sputtered Cu coatings, J. A. Thornton: J. Vac. Sci. Technol., 12 (1975) 830-835 8. Preparation and characterization of palladium-based composite membranes by electroless plating and magnetron sputtering, H.-B Zhao, G.-X. Xiong, G. V. Baron, Catalysis Today 56 (2000) 89-96

It is an object of the present invention to provide an integrated hydrogen separation membrane in which the structural, compositional, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer are gradually and continuously changed to produce an inclined integrated hydrogen separation membrane, The present invention provides a method for producing a support-integrated hydrogen separation membrane that exhibits excellent durability in an extremely commercialized atmosphere.

Also, it is intended to provide a support-integrated hydrogen separation membrane having a densified / porous composite structure in which structural, compositional, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer gradually and continuously vary.

Further, it is intended to provide a method of manufacturing a hydrogen separation membrane which is compatible with each other, the series of preliminary processes are simple and reproducible, regardless of the kind of the porous metal support or the alloy element of the hydrogen separation layer.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

The object of the present invention is achieved by preparing a support-integrated hydrogen separation membrane by multi-coating a hydrogen separation layer on the surface of a porous support, and utilizing the support-integrated hydrogen separation membrane thus produced in a hydrogen separation and purification process.

According to an aspect of the present invention, there is provided an integrated hydrogen separation membrane characterized in that structural, combinational, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer are gradually and continuously changed to form an inclined integrated hydrogen separation membrane, Provided is a method for producing a support-integrated hydrogen separation membrane exhibiting excellent durability in an extremely long commercialized atmosphere.

According to another aspect of the present invention, there is provided a porous support comprising a metal or an alloy; A plurality of open pores are formed, and an interface formed on the porous metal support; And a hydrogen separation layer of a palladium or palladium alloy formed on the interface, wherein the structural, compositional, and functional properties of the porous support, the interface, and the hydrogen separation layer are gradually and continuously changed and graded And a support-integrated hydrogen separation membrane.

Provided is a support-integrated hydrogen separation membrane which can maximize both hydrogen selectivity and permeability at the same time, is simple, efficient in manufacturing process, excellent in reproducibility even in a large area, and has high mass productivity, and a method for manufacturing the same .

That is, the production method of the present invention is not limited to the metal species of the porous support or the palladium alloy hydrogen separation layer composed of the metal or the alloy, and can be applied to the porous support by multi-coating of the sputtering method and low temperature heat treatment, The separator can be manufactured, which is advantageous in that it is efficient and the manufacturing process can be simplified.

It also exhibits a series of features consisting of a porous support, an interface and a hydrogen separation layer, exhibiting a composite structure such as a dense surface of a hydrogen separation layer and a porous internal structure, a maximum permeation saturation alloy composition, The structural, compositional and functional properties of the composite layer of the composite membrane of the present invention exhibit an inclined property to form a support-integrated hydrogen separation membrane, thereby further enhancing the high-temperature and high-pressure durability.

Furthermore, the hydrogen separation membrane according to the present invention can be widely applied not only to high purity hydrogen production, but also to various processes such as simultaneous reaction separation for hydrogen separation and purification, coal gasification combined cycle, carbon dioxide capture and storage, and the like.

FIG. 1 shows the problems and limitations of the hydrogen separation membrane (porous support / interface / hydrogen separation layer) produced by the prior art.
FIG. 2 is a schematic view of a support-integrated hydrogen separation membrane according to an embodiment of the present invention and structural, compositional and functional inclination characteristics of a support-integrated palladium-silver alloy hydrogen separation membrane manufactured according to an embodiment of the present invention.
FIG. 3 illustrates a surface state of a porous metal support according to a surface treatment process according to an embodiment of the present invention.
Figure 4 shows the structural, compositional and functional properties of a hydrogen separation layer prepared according to one embodiment of the present invention. (a) shows a composite structure (dense / porous) characteristic and (b) shows a stabilized alloy characteristic.
FIG. 5 shows the structural, compositional, and functional properties of the hydrogen separation membrane interface fabricated in accordance with one embodiment of the present invention. (a) shows the open interface and (b) shows the diffusion barrier / junction enhancement / gradient functional interface.
6 shows durability and hydrogen permeation selectivity characteristics of a palladium-gold alloy hydrogen separation membrane produced according to an embodiment of the present invention.
FIG. 7 shows the durability and hydrogen permeability selectivity of a palladium-silver alloy hydrogen separation membrane produced according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and particular embodiments are illustrated in the drawings and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are intended to specify the presence of stated features, integers, steps, operations, components, parts, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Hereinafter, embodiments of a support-integrated hydrogen separation membrane and a method of manufacturing the same according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings, wherein like reference numerals refer to like elements, And a detailed description thereof will be omitted.

For the sake of convenience of explanation, the direction of each constitution is based on the direction shown in the figure. However, the description based on such a direction is merely an example of the operating state, and the support-integrated hydrogen separation membrane according to the present embodiment and the method for manufacturing the same are not limited.

In order to be widely applied not only to the hydrogen purification field but also to the hydrogen separation process, the reaction separation and simultaneous process, the coal gasification combined power generation, and the capture and storage of carbon dioxide, the hydrogen selectivity and the permeability should be improved simultaneously. The durability of the separator must be improved, and the reproducibility of the functional aspect under a large area as well as the manufacturing yield must be improved. The hydrogen selectivity and the permeability of the hydrogen separation membrane are difficult to satisfy at the same time because they require the requirements of the separation membrane which are opposite to each other. Therefore, it is necessary to refine the syngas into a hydrogen separation membrane and to separate the hydrogen separation process into the hydrogen separation process and the hydrogen separation process which require hydrogen permeability. Hydrogen separation membranes with improved hydrogen selectivity and permeability have not been developed for use in a wide range of applications for the hydrogen economy as an energy source.

From the viewpoint of durability of the hydrogen separation membrane, the hydrogen separation membrane complex composed of the porous support, the interface and the hydrogen separation layers is composed of the metal and the ceramic combined body, each of which constitutes an independent constituent and lacks mutual physical and chemical affinity, The durability of the separator is remarkably poor under a high-pressure commercialization atmosphere. In addition, since the production process of the separation membrane is complicated and the process is made in a lack of mutual compatibility, it is mixed with dry and wet processes and is manufactured in an exposed atmosphere of impurities and air pollution, The yield is also low.

FIG. 1 shows the problems and limitations of the hydrogen separation membrane manufactured by the conventional technique, and the problems of the conventional manufacturing method are shown by dividing the porous metal support, the interface and the hydrogen separation layers, which are components of the hydrogen separation membrane composite. The porous support has a role of supporting the hydrogen separation layer mechanically and is made porous so that the permeation of hydrogen is smooth and a substrate functioning to uniformly coat the hydrogen separation layer should be performed. Since such a porous metal support exhibits a large number of macropores and uneven and rough surface roughness on the surface thereof, the surface of the separation membrane coated on the surface of the support is degraded in hydrogen selectivity due to the presence of many pores, When the thick separating layer is coated to remove the hydrogen permeation resistance due to the thickness, the functionality of the hydrogen permeability is drastically lowered. Therefore, a surface treatment process which can embed macropores existing on the surface of the porous support and planarize the surface roughness is indispensable. The accompanying problems of the prior art are shown in Fig. The large surface pores of the porous metal support are buried using ceramic powder, which indicates that the separation membrane is broken due to poor chemical affinity between ceramic and metal in a future heat treatment process or a high temperature commercialization atmosphere. In addition, the surface porosity, size, and surface roughness of the porous metal support are uneven. In addition, since conventional surface treatment processes are complicated and incomplete, the reproducibility of the process is very poor and thus limits the manufacture of the separator.

The hydrogen separation layer is mainly composed of a palladium alloy membrane having a function of selectively separating hydrogen. As the hydrogen selectivity and the functionality of the permeability are improved simultaneously, a stable palladium alloy should be maintained in a high temperature and high pressure commercial atmosphere. As discussed above, hydrogen selectivity and permeability are required to be different from each other, but it is difficult to realize a multi-layer structure capable of satisfying the requirements. Also, since the microstructure and compositions of the separation layer are not stable due to thermal changes, The problem of the prior art in which the durability is remarkably reduced is specifically shown in Fig.

The interface between the porous support and the hydrogen separation layer is an important part that determines the thermo-physico-chemical reaction and the adhesion force of the layers, and the adhesion of the support and the separation layer, the hydrogen permeability, But also significantly affects the durability of the membrane as well as the membrane. Among the conventional membrane fabrication techniques, the technology related to the above interface is very poor. The resistance effect of hydrogen permeability due to membrane breakage and closed interface state due to deterioration of adhesion, which is a fundamental problem accompanying the above, is shown in FIG.

The inventors of the present invention have found that by constructing an inclined integrated hydrogen separation membrane by gradually and continuously changing the structural, compositional, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer by a multi-sputter coating and a low temperature heat treatment process , A uniform solid solution having excellent adhesive strength is formed, and hydrogen selectivity and hydrogen permeability are improved at the same time, and a stable durability is achieved.

According to an aspect of the present invention, there is provided an integrated hydrogen separation membrane characterized in that structural, combinational, and functional properties of a porous support composed of a metal or an alloy and a hydrogen separation layer are gradually and continuously changed to form an inclined integrated hydrogen separation membrane, A method of manufacturing a support-integrated hydrogen separation membrane that exhibits excellent durability in an extremely long-term commercialized atmosphere can be provided.

Each of the sub-processes for producing the support-integrated hydrogen separation membrane has mutual compatibility, and a series of processes of surface treatment of the support, production of a hydrogen separation layer, and alloying heat treatment processes are simple, and the alloy type of the metal support or hydrogen separation layer The production process of the hydrogen separation membrane is superior to that of the conventional production method, and mass production of large area can be improved.

In addition, the support-integrated hydrogen separation membrane can improve not only the functionality of hydrogen permeability and hydrogen selectivity, but also the durability of the separation membrane and the reproducibility of the production method.

According to an embodiment of the present invention, there is provided a method of fabricating a porous substrate, comprising: a surface treatment step including surface pore filling by a metal powder on the porous support and surface planarization by pressing; Forming a hydrogen separation layer having a multi-functional dense / porous composite structure and a multi-layer structure by sputter coating at room temperature; And a step of heat-treating the porous support and the hydrogen separation layer at a low temperature of 550 ° C or less, thereby improving the hydrogen permeation selectivity and durability of the hydrogen separation membrane.

According to an embodiment of the present invention, the surface treatment step of the porous support may include a step of treating the surface of the porous support with a support microparticulate powder of not more than several microliters for selectively embedding large surface pores of several to several tens of microns or more existing on the surface of the porous support, Vacuum embedding of nanocomposite copper or silver powders for selectively embedding vacancies of the micropores and micro-surface pores of a few microns or less existing on the surface of the porous support; And a step of planarizing the surface of the porous support using a press.

According to one embodiment of the present invention, the nanocomposite copper or silver powders buried during the surface treatment step of the porous support may be subjected to a subsequent vacuum of 1.0 x 10 ^-2 torr to 760 torr, The hydrogen permeability of the hydrogen separation membrane can be improved by forming an open interface composed of micropores by diffusion, reaction, and re-sintering of the nano-sized powders by a low temperature heat treatment at 550 캜.

According to an embodiment of the present invention, the step of forming the hydrogen separation layer may include a step of forming a hydrogen separation layer by applying a multi-functional sputtering material at a high temperature of from 5.0 × 10 ^-5 torr to 5.0 × 10 ^-3 torr, A dense surface structure for maximizing hydrogen selectivity of the hydrogen separation membrane; And an inner porous film for maximizing the hydrogen permeability of the hydrogen separation membrane formed using a multifunctional sputtering process at room temperature, a low vacuum of 5.0 × 10 ^-3 torr to 5.0 × 10 ^-1 torr, and a low power process condition of 10 W to 100 W Structures can be selectively formed to improve hydrogen selectivity and hydrogen permeability at the same time.

According to an embodiment of the present invention, the step of forming the hydrogen separation layer may include a step of forming silver (Ag) at a high temperature of room temperature, a high vacuum of 5.0 × 10 ^-5 torr to 5.0 × 10 ^-3 torr, (Fe) or nickel (Ni), which is a main component of the porous stainless steel or nickel support, and a silver coating layer of a dense structure constituting the self-hydrogen separation layer by sputtering, By maintaining the saturated compositions of the hydrogen separation layer at the development and commercialization temperatures, surface diffusion of the support components can be suppressed without the addition of diffusion barrier films of new materials.

According to an embodiment of the present invention, the step of forming the hydrogen separation layer may include a step of forming a hydrogen separation layer by using a high-vacuum process conditions of room temperature, 5.0 x 10 ^-5 torr to 5.0 x 10 ^-3 torr, high power process conditions of 120 W to 300 W, A palladium layer and at least one alloy selected from the group consisting of silver, gold, copper, nickel, ruthenium, and yttrium under low vacuum conditions of 10 ^-3 torr to 5.0 10 ^-1 torr and low power of 10 W to 100 W The metal layers are formed by controlling the thickness of the metal layers by using a plurality of coating layers having a dense structure and a porous structure, respectively, and the heat treatment at the low temperature is performed in a vacuum of 1.0 x 10 ^-2 torr to 760 torr, By performing the low temperature heat treatment at 400 ° C to 550 ° C, it is possible to maximize the hydrogen permeability of the hydrogen separation membrane by maintaining the maximum permeation saturated alloy composition.

According to an embodiment of the present invention, by forming the dense / porous composite separating layer structure, the maximum permeable saturated alloy composition, the hydrogen separation layer having the diffusion preventing function and the open interface together by the room temperature sputtering step and the low temperature heat treatment step Hydrogen selectivity and hydrogen permeability can be improved at the same time.

According to one embodiment of the present invention, the integrated material characteristics of the porous support and the hydrogen separation layer, the standardized whole process composed of compatible detailed processes, and the kind and surface state of the porous support, So that reproducibility and mass productivity of the hydrogen separation membrane can be improved.

According to an embodiment of the present invention, the integrated characteristics of the porous support and the hydrogen separation layer and the interfacial characteristics composed of the interconnected structures of the porous support and the hydrogen separation layer, Can improve the durability of thermal, chemical, and mechanical stability.

According to an embodiment of the present invention, the alloy of the hydrogen separation layer may include, but is not limited to, palladium / silver, palladium / gold, palladium / copper, palladium / nickel, palladium / ruthenium, and palladium / One or more can be selected from the group.

According to one embodiment of the present invention, the metal of the porous support may be selected from the group consisting of stainless steel, nickel, vanadium, tantalum, and titanium, but not limited thereto.

According to an embodiment of the present invention, the method of manufacturing the hydrogen separation membrane can be applied to a plate-like separation membrane of 3 inches or more or a tubular separation membrane of 10 inches or more, thereby improving the mass production of large area and efficiency of the manufacturing process.

According to another aspect of the present invention, there is provided a porous support comprising a metal or an alloy; A plurality of open pores are formed, and an interface formed on the porous metal support; And a hydrogen separation layer of a palladium or palladium alloy formed on the interface, wherein the structural, compositional, and functional properties of the porous support, the interface, and the hydrogen separation layer are gradually and continuously changed and graded A support-integrated hydrogen separation membrane may be provided.

The support-integrated hydrogen separation membrane exhibits an inclined property as the structural, compositional, and functional properties of the porous support and the hydrogen separation layer progressively and continuously change, so that the hydrogen separation membrane is integrated. As a result, thermal, chemical and mechanical stability It is possible to improve the durability.

The support-integrated hydrogen separation membrane according to an embodiment of the present invention may further include a silver (Ag) coating layer between the porous support and the hydrogen separation layer to suppress the surface diffusion of the porous support metal and maintain the maximum permeation saturated alloy composition .

According to one embodiment of the present invention, the composition of the maximum permeable saturated alloy of the hydrogen separation layer may be, but is not limited to, palladium: silver = 77: 23, palladium: gold = 95: 5, = 60: 40.

In the support-integrated hydrogen separation membrane according to one embodiment of the present invention, the metal of the porous support may be dissolved in the palladium or palladium alloy between the porous support and the hydrogen separation layer to form a uniform solid solution at the interface.

The support-integrated hydrogen separation membrane can be widely applied not only to the field of hydrogen purification but also to industry such as hydrogen separation field.

Hereinafter, the present invention will be described in more detail with reference to the following examples of the support-integrated hydrogen separation membrane and method of the present invention.

[ Example  One]

Palladium in accordance with one embodiment of the invention the porous nickel support method of producing gold alloy hydrogen separation membrane is added to 500 to 1000 pressure kgf / cm ² for nickel powder having an average diameter of 3μm as a compression press forming machine diameter disk form of a two-inch Molded. In order to increase the thermal stability and the mechanical strength of the porous nickel metal support produced by the compression press machine, it was heat-treated at 900 ° C for 2 hours in a reducing atmosphere.

The prepared 2 inch sized porous nickel supports were fixed to a specimen holder of an automatic polishing machine capable of constant pressure regulation and uniform rotation. The polishing part of the specimen and the polishing pad were always parallel and uniformly polished, and the influence of the uniaxial polishing during polishing was minimized. The irregular waviness appearing in the polishing process causes polishing of relatively large particles to cause scratches on the surface of the specimen surface or to lower the uniformity of the surface. Therefore, the formation of the complex structure of the hydrogen separation layer according to the present invention may be prevented, The thickness of the layer causes the surface pores to be generated during the production of the thin separation membrane.

The porous nickel support was subjected to a rough grinding process using # 1000 to # 4000 silicon carbide abrasive paper to remove surface roughening and foreign substances existing on the surface of the support.

A nickel metal powder having an average particle size distribution of 0.1 μm to 5 μm on the surface of the initially polished porous nickel metal support and exhibiting excellent chemical affinity with the palladium alloy component and having the same metal as the support metal, The macropores on the surface of the support were selectively buried through a vacuum filling method and the surface of the support was planarized. Next, in order to embed micro pores of a few micrometers or less remaining on the surface, silver (Ag) nano powder having an average particle size distribution of 0.025 탆 to 0.1 탆 was diluted with deionized water (DI water) To fill the surface micropores. The vacuum-buried metal powders can facilitate the diffusion and sintering reactions at the interface as palladium, support, and metal powder particles are diffused in a subsequent low-temperature heat treatment process to easily form an open structure. In addition, since the buried metal powder is buried in the pores sequentially by the pressure flow, the vacuum filling method has advantages such as simplicity and excellent reproducibility than the conventional powder filling method.

Finally, the surface of the support was planarized using a press surface treatment method at a pressure of 10 kgf / cm ² to 50 kgf / cm ² for less than 2 seconds to 5 minutes. The press planarization surface treatment process was relatively simple in comparison with the conventional wet micro polishing process, and was simple and reproducible regardless of the surface state of the support.

Next, a polyvinyl alcohol brush was used to clean impurities and foreign substances that may occur during the surface treatment of the support, and chemical contaminants were removed using NH ₄ OH or SC-1 (Standard Clean-1) solution. Finally, a submicron sized impurity particle was removed using Megasonic sonication, and then a vacuum dryer was used for 2 hours or more at a temperature range of about 60 ° C to about 100 ° C to remove surface impurities adsorbed on the support.

Next, a plasma surface treatment process was performed to remove impurities on the surface of the porous nickel substrate and to activate the surface. Plasma surface treatment is about 1.0 × 10 ^-3 torr of flow gives the base pressure and about 1.0 × 10 ^-1 torr for about 30sccm (Standard Cubic Centimeter per Minutes) to about 50sccm hydrogen gas at a process pressure of about 13.56MHz at room temperature The surface of the porous nickel metal support was modified for about 5 to 15 minutes at a discharge excitation AC power frequency of about 100 W to about 200 W alternating voltage or a direct current voltage of about 350 W to about 500 W. Plasma surface treatment process and the sputtering process is in-proceeds in situ (in -situ) the vacuum method, a sputtering process was a multi-coating to a continuous metal such as palladium and gold on top of the porous nickel metal substrate surface treated.

Palladium sputtering process is from about 10W to about 100W of direct-current power supply, of about 10sccm to about 30sccm of argon gas, of about 5.0 × 10 ^-3 torr to about 5.0 × 10 ^-1 torr of chamber pressure, palladium, under conditions set to substrate temperature of room temperature To a thickness of 2 to 3 m.

The silver sputter process for preventing the diffusion of the support metal component continuously includes a direct current power source of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 × 10 ^-5 torr to about 5.0 × 10 ^-3 torr , And a coating temperature of 0.1 to 1 占 퐉 in thickness of silver under a condition set at a substrate temperature of room temperature.

Continuously under the conditions set at a direct current power of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 x 10 ^-5 torr to about 5.0 x 10 ^-3 torr, and a substrate temperature of room temperature, Was coated at a thickness of 1.5 to 2.5 占 퐉.

Next, the gold sputtering process is performed under conditions set at a substrate temperature of room temperature, a process gas pressure of about 5.0 × 10 ^-4 torr to about 2.0 × 10 ^-3 torr, a direct current power of about 20 W to about 60 W, an argon gas of about 10 sccm to about 30 sccm, And a microcrystallized gold metal coating film was deposited to form a stable alloyed and dense microstructure in a subsequent low temperature heat treatment process.

And finally setting the substrate temperature to a substrate temperature of room temperature, a direct current power of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 x 10 ^-5 torr to about 5.0 x 10 ^-3 torr, To 0.1 to 1 mu m.

As the hydrogen separation layer of the porous or dense fine structure is formed according to the respective sputter process parameters, the palladium and gold sputter process progressively progresses from the upper part to the lower part of the surface of the palladium alloy coating layer gradually, So that the oblique characteristic can be expressed.

After completion of the sputter multi-coating process, a vacuum degree of about 760 torr (atmospheric pressure) to 1.0 x 10 < ^-2 > torr in a vacuum furnace in a hydrogen reduction atmosphere, and a temperature of about 400 & C for 1 hour to 2 hours to alloW the separation layer and to form the composite structure and the reaction of the metal components of the sputter coated palladium, the buried support itself, and the buried metal powder particles are activated The interfacial adhesion was improved by facilitating the diffusion at the interface of the separator.

As a result of the thermal fatigue test and the thermal shock endurance test at 500 ° C. for 3000 hours, the weight fraction of the surface metal components of the palladium-gold alloy hydrogen separation membrane prepared as described above formed a saturated composition, I did. In addition, the microstructure of the surface of the separator has been densely and steadily alloyed, and hydrogen permeability and hydrogen permeability were both maximized at the same time as the hydrogen separation layer had a composite structure of dense quality and porous structure. It was possible to obtain a hydrogen separation membrane having improved durability at a high temperature by minimizing the surface diffusion of the support component.

Therefore, the hydrogen separation membrane according to an embodiment of the present invention can be applied to a hybrid thin film / porous composite membrane due to each of the detailed processes having mutual compatibility, such as a simple surface treatment, a room temperature functional sputtering method and a low temperature heat treatment process, Structure, maximum permeation saturation composition, diffusion barrier, and open interfaces together, the durability of the membrane as well as the reproducibility of the manufacturing method were improved at the same time as the functionality of the hydrogen permeability selectivity. Also, as the structural, compositional, and functional properties of the porous support and the hydrogen separation layer progressively and continuously change, they exhibit sloping characteristics, and the hydrogen separation membranes are integrated so that the durability of thermal, chemical, and mechanical stability is greatly improved.

[ Example  2]

A porous stainless steel support (PSS-316L; Mott Metallurgical Corporation) having a diameter of 2 inches was used as a manufacturing method of the palladium-silver alloy hydrogen separation membrane according to an embodiment of the present invention.

The 2-inch porous stainless steel supports were fixed to a specimen holder of an automatic polishing machine capable of constant pressure regulation and uniform rotation. The polishing part of the specimen and the polishing pad were always parallel and uniformly polished, and the influence of the uniaxial polishing during polishing was minimized. The irregular waviness appearing in the polishing process causes polishing of relatively large particles to cause scratches on the surface of the specimen surface or to lower the uniformity of the surface. Therefore, the formation of the complex structure of the hydrogen separation layer according to the present invention may be prevented, The thickness of the layer may cause surface pores to be generated during the production of the separation membrane.

The porous stainless steel support was subjected to a rough grinding process using # 1000 to # 4000 silicon carbide abrasive paper to remove surface roughness and foreign matter on the surface of the support.

Stainless steel metal powders having an average particle size distribution of 0.1 μm to 5 μm on the surface of the micro-polished porous stainless steel support and exhibiting a good chemical affinity with the palladium alloy component and having the same metal as the support metal were subjected to DI water And the macro pores on the surface of the support were selectively embedded through the vacuum filling method, and the surface of the support was planarized. Next, silver (Ag) nano powder having an average particle size distribution of 0.025 탆 to 0.1 탆 is diluted in DI water to embed micro pores of several micro or less remaining on the surface, and the surface micro-pores Respectively. The vacuum-buried metal powders can facilitate the diffusion and sintering reactions at the interface as palladium, support, and metal powder particles are diffused in a subsequent low-temperature heat treatment process to easily form an open structure. In addition, since the buried metal powder is buried in the pores sequentially by the pressure flow, the vacuum filling method has advantages such as simplicity and excellent reproducibility than the conventional powder filling method.

Finally, the surface of the support was planarized using a press surface treatment method at a pressure of 10 kgf / cm ² to 50 kgf / cm ² for less than 2 seconds to 5 minutes. The press planarization surface treatment process is relatively simple in comparison with the conventional wet micro polishing process, and is simple and reproducible regardless of the surface state of the support.

Next, a polyvinyl alcohol brush was used to clean impurities and foreign substances which may be formed during the surface treatment of the support, and chemical contaminants were removed using NH ₄ OH or SC-1 solution. Finally, a submicron sized impurity particle was removed using Megasonic sonication, and then a vacuum dryer was used for 2 hours or more at a temperature range of about 60 ° C to about 100 ° C to remove surface impurities adsorbed on the support.

Next, a plasma surface treatment process was performed to remove impurities on the surface of the porous stainless steel support and to activate the surface. Plasma surface treatment is about 1.0 × 10 ^-3 torr with a base pressure of about 1.0 × 10 ^-1 torr gives the process pressure of the flow of hydrogen gas of about 30sccm to about 50sccm, a discharge of about 13.56MHz at room temperature where the AC power supply frequency, The surface of the porous stainless steel support was modified at an AC voltage of about 100 W to about 200 W or a DC voltage of about 350 W to about 500 W for about 5 to 15 minutes. The plasma surface treatment process and the sputtering process were conducted in an in-situ vacuum process, and the sputtering process continuously coated palladium and silver metals on top of the surface-treated porous stainless steel support.

Palladium sputtering process is from about 10W to about 100W of direct-current power supply, of about 10sccm to about 30sccm of argon gas, of about 5.0 × 10 ^-3 torr to about 5.0 × 10 ^-1 torr of chamber pressure, palladium, under conditions set to substrate temperature of room temperature To a thickness of 1 to 3 mu m.

The silver sputter process for preventing the diffusion of the support component is then performed using a DC power source of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 × 10 ^-5 torr to about 5.0 × 10 ^-3 torr, A step of coating the thickness of silver to 0.1 to 1 m under conditions set at a substrate temperature of room temperature.

Subsequently, the palladium sputtering process may be carried out under conditions of a direct current power of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 × 10 ^-5 torr to about 5.0 × 10 ^-3 torr, A process of coating the thickness of palladium to 2 to 3 m was carried out.

The silver sputter process is then performed under conditions set at a DC power source of 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 x 10 ^-5 torr to about 5.0 x 10 ^-3 torr, And the thickness of silver was 0.1 to 1 m. A microcrystallized silver metal coating was deposited to form stable alloying and dense microstructure in the subsequent low temperature heat treatment process.

Finally, the palladium sputter process may be carried out under conditions of a direct current power of about 120 W to about 300 W, an argon gas of about 10 sccm to about 30 sccm, a process pressure of about 5.0 x 10 ^-5 torr to about 5.0 x 10 ^-3 torr, To a thickness of 0.1 to 1 mu m.

The above-mentioned palladium and silver sputtering processes are characterized in that the hydrogen separation layers of porous or dense fine structure are formed by the respective sputtering process parameters, and the structural, compositional and functional properties gradually increase from the upper part to the lower part of the surface of the palladium alloy coating layer, So that the oblique characteristic can be expressed.

After completion of the sputter multi-coating process, a degree of vacuum of about 760 torr (atmospheric pressure) to 1.0 x 10 < ^-2 > torr in a vacuum furnace in a hydrogen reduction atmosphere, and an annealing temperature of about 450 & C for 1 hour to 2 hours to alloW the separation layer and to form the composite structure and the reaction of the metal components of the sputter coated palladium, the buried support itself, and the buried metal powder particles are activated The interfacial adhesion was improved by facilitating the diffusion at the interface of the separator. In addition, the silver metal components minimize the diffusion of the iron components of the support to the surface by competitive diffusion as they form a dense intermediate layer by sputter coating.

As a result of the thermal fatigue test and the thermal shock endurance test at 500 ° C. for 3000 hours, the weight fraction of the surface metal components of the palladium-gold alloy hydrogen separation membrane prepared as described above formed a saturated composition, I did. In addition, the microstructure of the surface of the separator has been densely and steadily alloyed, and hydrogen permeability and hydrogen permeability were both maximized at the same time as the hydrogen separation layer had a composite structure of dense quality and porous structure. It was possible to obtain a hydrogen separation membrane having improved durability at a high temperature by minimizing the surface diffusion of the support component.

Therefore, the hydrogen separation membrane manufactured according to the present invention has a complicated thin film structure of dense / porous structure due to the respective processes which are compatible with each other, such as a simple and highly reproducible supporter surface treatment process, a room temperature functional sputtering process and a low temperature heat treatment process, By simultaneously forming the maximum permeation saturation composition, diffusion barrier and open interfaces, the durability of the membrane as well as the reproducibility of the preparation method were improved at the same time as the functionality of the hydrogen permeation selectivity. Also, as the structural, compositional, and functional properties of the porous support and the hydrogen separation layer progressively and continuously change, they exhibit sloping characteristics, and the hydrogen separation membranes are integrated so that the durability of thermal, chemical, and mechanical stability is greatly improved.

FIG. 2 is a schematic view of a support-integrated hydrogen separation membrane according to the present invention and a structural, compositional, and functional inclination characteristics of the support-integrated palladium-silver alloy membrane produced according to an embodiment of the present invention. In the conventional hydrogen separation membrane, the porous support, the interface and the hydrogen separation layers constituting the conventional hydrogen separation membranes form respective independent constituents and are incompatible with each other and are formed in complicated detailed processes. As a result, the functionality and durability of the separation membrane are insufficient, It is not enough to commercialize it as a refining and separation field. As can be seen from the schematic diagram of FIG. 2, the present invention is characterized in that the structural, combinational and functional properties of the porous metal support and the hydrogen separation layer gradually change as the composition gradually changes, Not only the functionality of the selectivity but also the reproducibility of the production method is excellent and also exhibits excellent durability in a high temperature and high pressure commercial atmosphere. The reason for having excellent characteristics of the present invention will be described in detail with reference to FIG. 2 as follows.

First, considering the structural gradient, the surface of the hydrogen separation layer is composed of a dense structure using a functional sputter system, and a hybrid structure formed of a porous structure inside And the interface forms an open interface structure for smooth hydrogen flow without hydrogen permeation resistance. Finally, the porous metal support is composed of a porous structure composed of open pores. Therefore, it can be seen that the microstructural inclination characteristic is formed with increasing porosity toward the surface of the hydrogen separation layer, and the microstructural inclination characteristic becomes more and more porous toward the support layer, and the cross-sectional microstructure photograph of the Pd- SEM).

Secondly, considering the compositional gradient, the average weight fraction of palladium and silver components in the hydrogen separation layer is constant at 77:23, and the palladium component diffuses into the support layer, and at the interface, the porous stainless steel support (PSS: Porous Stainless Steel support is mixed with iron, which is the main component of steel, and the iron, which is a support component, diffuses into the hydrogen separation layer to form a solid solution, thereby improving the adhesion at the interface. So that solid solution can not be formed and diffusion to the separation layer no longer occurs. Therefore, it can be confirmed from the cross-sectional EDS composition results of FIG. 2 that the synergistic inclination is exhibited at the interface by mutual diffusion.

Thirdly, considering the functional gradient, the hydrogen separation layer can improve the hydrogen selectivity and permeability simultaneously by forming the complex microstructure of the dense / porous structure, and the dense palladium / Can further enhance the hydrogen permeability of the separating layer by preventing the diffusion of the support component from the multiple coating layers and having the maximum permeable alloy composition (weight ratio of palladium to silver being 77:23) By forming the interface, the permeation of hydrogen through the support layer is facilitated. By forming the inclined solid solution at the interface, the adhesion between the support and the separating layer is improved, thereby providing excellent durability of the separator under high temperature and high pressure commercialization conditions. Structural, tectonic, and functional gradients are used to describe extreme external atmosphere changes The durability of the separator is significantly improved as the stable separation membrane functionality is maintained.

Fourth, because of its structural, compositional, and functional tilting characteristics, it is compatible with the detailed processes because it exhibits integrated membrane characteristics, and each process is simple, and the reproducibility is improved by the standardization process which is independent of the types of porous metal support and hydrogen separation layer alloys. Accordingly, the production efficiency of the support-integrated hydrogen separation membrane of the present invention is very excellent, and thus it is suitable for commercialization.

The manufacturing process and characteristics of the support-integrated hydrogen separation membrane of the present invention will be described in detail as follows.

As a requirement for the production of the support-integrated hydrogen separation membrane, the support and the hydrogen separation layer must have excellent physical and chemical affinity and have integrated material characteristics. Therefore, it is necessary to use a support of the same kind of metal or alloy which is excellent in affinity with the palladium alloy as the hydrogen separation layer. Stainless steel and nickel satisfying the above requirements are known as typical porous supports. The porous metal support exhibits uneven rough surface roughness with macropores of tens of microns in surface area (FIG. 3). This results in a dense hydrogen separation layer of palladium alloy coated on top of it, or a low hydrogen selectivity due to the presence of pores and defects in the film layer. On the other hand, if the coating layer is thicker than a few micrometers in thickness in order to embed the surface pores of the coated membrane, the functionality of the hydrogen permeability having a characteristic inversely proportional to the membrane thickness is significantly deteriorated. Therefore, a surface treatment process for controlling macropores to a few micrometers or less and planarizing the surface roughness is indispensable. The surface treatment of the conventional support surface is complicated and the surface porosity, pore size and surface roughness of the surface-treated porous metal support are not uniform and the reproducibility is insufficient. As the surface pore filling and flattening of the support are perfect, And acts as a resistance against permeation of hydrogen to lower hydrogen permeability. The surface treatment process of the present invention is shown stepwise in FIG. 3 so as to solve the above problems and to have integrated membrane characteristics.

3 shows the surface state of the support according to the surface treatment process of the porous metal support of the present invention. A rough grinding process using a silicon carbide abrasive paper was performed to remove surface roughness and foreign substances existing on the surface of the porous metal support. In order to embed surface pores having a size of several tens of micrometers or more, Powder (stainless steel or nickel) was diluted only in deionized water (DI water) to minimize foreign matter contamination, and the above large pores were sequentially filled using a vacuum embedding method. By using the same kind of metal powder, it is possible to prevent destruction of the separation membrane ultimately resulting from bad affinity with the palladium alloy separation layer by the ceramic powder, and it is possible to satisfy the integrated requirement of the metal material. In addition, since it is possible to selectively fill in the order of macropores by the vacuum embedding method, the reproducibility is superior to that of the conventional embedding method. Pores of several micrometers or less remaining on the surface are subjected to selective embedding of micropores by using the above-mentioned vacuum embedding method using copper (Cu) or silver (Ag) nano powders. The buried copper and silver nanopowder particles are then activated by subsequent heat treatment to react with the sputtered nanoparticulate particles or sinter reaction with the support particles to form an open structure at the interface thereby facilitating hydrogen permeation through the open interface . While the conventional open interfacial technology (KR 10-1459673) involves a high temperature heat treatment process and the open interfacial process is complicated and lacks reproducibility, the process of the present invention is open by a simple process by diffusion of nanoporous or silver particles Since the interface is formed, the reproducibility is excellent.

Finally, by performing surface flattening of the support using a simple press surface treatment method, excellent average surface roughness of 0.183 탆 was maintained as seen from the Confocal Laser Scanning Microscope (CLSM) result of Fig. The above-mentioned press planarizing surface treatment process is relatively simple in comparison with the conventional complicated fine polishing wet process (KR 10-1459673, KR 10-1271394, KR 10-1176585), it is independent of the surface state of the support and is simple and reproducible great. Such a planar surface condition can provide uniform nanopalladium nucleation by subsequent sputtering processes. The support surface treatment process of the present invention is a simple process that is not dependent on surface porosity, pore size and surface roughness of a metal support, as compared with the conventional surface treatment process, and is excellent in reproducibility and can be used as a standardization process for mass production. From the viewpoint of the functionality of the hydrogen separation membrane, the hydrogen permeation selectivity of the hydrogen separation layer can be further improved because the open interface at low temperature and nanopalladium nucleation of the functional sputter can be easily produced.

Figure 4 shows the structural, compositional, and functional properties of a palladium alloy hydrogen separation layer produced by a functional sputter process according to the present invention. The hydrogen selectivity and the permeability are required to satisfy the requirements of the separating layer which is contrary to each other. Since the conventional hydrogen separation layer forms a uniform independent structure (dense structure or porous structure) regardless of the coating method, the functionality of only one of hydrogen selectivity or hydrogen permeability can be selectively increased, It has not been widely commercialized in the separation field. In order to solve the above problems, a multi-coated hydrogen separation layer having respective functionalities (dense structure, porous structure, diffusion preventing layer) as shown in FIG. 2 was prepared using a functional magnetron sputtering method . A complex structure of the surface for maximizing the hydrogen selectivity using a room temperature / high vacuum / high power sputterer and a porous structure for improving the hydrogen permeability using a room temperature / low vacuum / low power sputter hybrid structure can be selectively formed irrespective of the kind of palladium alloy, and hydrogen selectivity and permeability, which can not be obtained by conventional separators, can be improved at the same time (FIG. 4). Further, the diffusion density of the self-hydrogen separation layer can be improved by forming a diffusion barrier film using a phase separation phenomenon between the (Ag) coating layer and iron (Fe), which is a main component of the stainless steel support, And the composition of the separation layer is controlled by controlling the thickness of the coating layer of the sputter. Thus, a stable maximum transmission alloy composition can be obtained in the low-temperature heat treatment. FIG. 4 shows the maximum permeable alloy composition and stable fine particle separation layer for each palladium alloy produced according to the present invention, and the hydrogen permeability and durability of the separator can be improved due to the above characteristics. The hydrogen separation layer forming process according to the present invention is a standardization process that can provide multifunctionality of the separation layer by sputter multi coating regardless of the kind of the palladium alloy as compared with the conventional process and can be used as a selective combination of dense / It is possible to improve the hydrogen selectivity and permeability simultaneously by forming a hydrogen separation layer which is easy to structure, can form a diffusion barrier, control the maximum permeable alloy composition by multiple coating thickness, and has stable microstructure and alloy composition in a low temperature heat treatment process. And it has excellent durability even under commercialization conditions.

FIG. 5 shows the structural, compositional, and functional properties of the hydrogen separation membrane interface fabricated by the present invention. Since the hydrogen separation membrane is composed of a porous support coated with a palladium alloy membrane, which is a hydrogen separation layer, the interface represented by the boundaries of the layers has a very important influence on not only the functionality but also the durability characteristics of the membrane. The development of the interface has not been developed until now and it has been published in some literatures only by the present inventors (patent: KR 10-1459673, KR 10-1271394, papers: Development of Pd alloy hydrogen separation membranes with dense / porous J Kim, SH Kim, DW Kim: Advanced in Materials Science and Engineering, 438216 (2014), Improvement in Long-term Stability of Pd Alloy Hydrogen Separation Membranes, CH Kim, JH Lee , ST Jo, DW Kim, J. Kor. Inst. Surf. Eng., 48 (2015) 11-22)

In order to form a dense palladium thin film which improves the functionality of hydrogen selectivity on the porous support, the pore filling and flatness of the support surface must be maintained through the surface treatment process of the support as described above. Due to the surface treatment process and the dense palladium thin layer, the interface of the separation membrane is formed in a closed state, and when the hydrogen moves from the hydrogen separation layer to the support, it acts as a resistance of hydrogen permeation at the interface, thereby suppressing hydrogen permeation. Therefore, in order to increase hydrogen permeability, the interface structure must be formed into an open structure having a plurality of pore states. The present inventors have developed a process technology for improving the hydrogen permeability by forming an open interface through the activation of the high temperature reaction of the support fine particles and the palladium fine particles (Patent: KR 10-1459673, Development of Pd alloy hydrogen separation membranes with dense / porous hybrid structure for high hydrogen permselectivity., JY Han, CH Kim, SH Kim, DW Kim: Advanced in Materials Science and Engineering, 438216 (2014)). The separation membrane formed by the open interface compared to the closed interface exhibited a hydrogen permeability of more than 2 times at the same separation layer thickness, but it requires a high-temperature heat treatment process and also lacks the reproducibility of the process. The above problems must be solved.

In order to solve the above-mentioned problems, the present invention is characterized in that the nanoporous or silver powders are buried in the micro pores of the surface during the surface treatment process of the support as described above, and the diffusion, By forming the open interface of the fine pores by sintering, permeation of hydrogen can be smoothly carried out along with the fine pores remaining on the surface of the support which is not buried even by the surface modification step, and the hydrogen permeability can be improved. The open interface of the representative palladium-silver, palladium-gold and palladium-copper alloy separator prepared according to one embodiment of the present invention is shown in FIG. 5, and it can be confirmed that many fine pores are formed all over the interface. The open interface process manufactured according to one embodiment of the present invention can be formed at a low temperature of 550 ° C or less and is not dependent on the porous metal support or the palladium alloy and is highly reproducible by a simple process so that it can be applied to future commercialization processes .

Also, the interfacial state plays an important role in the adhesion between the support and the hydrogen separation layer, so that the hydrogen separation membrane has a considerable influence on the durability when it is commercialized. The most important characteristic of the present invention is to form a homogeneous solid solution by using an integrated metal or alloy, and to improve the durability of the hydrogen separation membrane by making structural, compositional and functional inclination characteristics. As shown in FIG. 5, the interface of the separation membrane is formed by a low-temperature heat treatment to form a palladium-nickel bonded solid solution interface in the case of PNS (Porous Nickel Support) between the porous metal support and the hydrogen separation layer, PSS (Porous Stainless Steel Support) forms a palladium-iron bonded solid solution interface, thereby enhancing the interfacial adhesion, and thus the durability of the separator is greatly improved even in an extremely commercialized atmosphere of high temperature and high pressure.

The support membrane of the present invention has an inclined characteristic as the porous support, the interface, and the hydrogen separation layer progressively and continuously change their structural, functional and functional properties, thereby improving not only the functionality of the hydrogen permeation selectivity, And has excellent durability even under high-pressure commercialization conditions. In order to confirm not only functionality but also stability and durability, the support-integrated hydrogenated membrane produced by the present invention was subjected to a thermal durability test at a high temperature commercialization temperature of 500 ° C for 3,000 hours as shown in FIG. As shown in FIG. 6 (a), thermal fatigue at 500 ° C / RT (room temperature) was repeatedly repeated every 200 hours, and severe thermal shock was applied thereto. The surface microstructure of the hydrogen- -SEM), the alloy structure (XRD) and the surface composition (EDS) are shown in Figs. 6 (b), (c) and (d). As can be seen from the results of FIG. 6, the microstructure of the separator was stable without minute changes owing to the integrated characteristics of the support and the hydrogen separation layer during 3000 hours at high temperature, It was confirmed that the separation membrane was a very stable palladium-gold alloy separation membrane by maintaining the saturation compositional alloy concentration of high permeability stably.

In order to confirm the hydrogen permeation selectivity of the palladium-gold alloy hydrogen separation membrane over a long period of time, hydrogen permeability and nitrogen permeability were measured for 3000 hours at a temperature of 6.8 atm and 500 ° C. under hydrogenation and nitrogen gas injection, respectively Is shown in Fig. 6 (e). As can be seen from the above results, the separator initially showed excellent hydrogen permeability at 2.07 × 10 ^-6 mol s ^-1 m ^-2 Pa ^-1 and nitrogen was not detected within the error range of the measuring equipment, It proved to be very good. The hydrogen and nitrogen permeabilities measured continuously for 3000 hours were almost insignificant compared with the initial measured values, so that the separator of the present invention exhibited stable hydrogen permeability selectivity.

From the above results, the support-integrated palladium-gold alloy hydrogen separation membrane has a dense / porous composite structure of a hydrogen separation layer having an ultra-thin thickness as described above with reference to FIG. 2 due to structural, Simultaneous enhancement of hydrogen selectivity and hydrogen permeability could be achieved by the maximum hydrogen permeable alloy composition, open interface structure with excellent adhesion, stable microstructure and coordination properties, and membrane durability was also improved.

FIG. 7 is a graph showing changes in microstructure, surface composition, and hydrogen permeation selectivity of a palladium-silver alloy hydrogen separation membrane in 3000 hours . The surface microstructure, alloy structure, surface composition, and hydrogen permeation selectivity of the palladium-silver alloy hydrogen separation membrane at 1000, 2000, and 3000 hours are shown in FIG. As can be seen from the results of the FE-SEM, XRD and EDS of FIG. 7, the microstructure of the separator was stable without any deformation or destruction due to the integrated characteristics of the support and the separating layer during 3000 hours in an extreme heat shock environment , And it was confirmed that the separator was made of a palladium-silver alloy film having a very stable saturation compositional alloy concentration (palladium: silver = 77: 23 weight fraction) without any diffusion of support components even at high temperatures there was.

In order to confirm the hydrogen permeation selectivity characteristic of the palladium-silver alloy hydrogen separation membrane over 3000 hours, the results are shown in FIG. 7 (e). As will be found from the result of the above, the separation membrane is initially ^{2.307 × 10 -6 mol s -1 m} -2 Pa - 1 exhibited a high hydrogen permeability, the nitrogen will hardly sense the excellent hydrogen selectivity of infinity . In addition, the hydrogen and nitrogen permeabilities measured continuously for 3000 hours were almost constant as compared with the initial measured values, and thus the functionality of the hydrogen permeation selectivity obtained in the hydrogen separator prepared by the present invention was very stable Could know.

As can be seen from the above results, the support-integrated palladium-silver alloy hydrogen separation membrane according to one embodiment of the present invention is characterized in that the metal-integrated nature of the support and the hydrogen separation layer, the formation of the multi- In addition to the membrane formations, simple selective and compliant processes that are not dependent on the type of porous metal support, the surface condition, and the type of palladium alloy, the hydrogen selectivity of the hydrogen- And the durability of the separator and the reproducibility of the production were remarkably improved.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention as defined in the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

The present invention can produce a support-integrated hydrogen separation membrane by a room temperature functional sputter process and a low temperature heat treatment process on a porous metal support without complicated pretreatment process, and it is also possible to improve the durability of the membrane and the reproducibility of the production method The support-integrated hydrogen separation membrane can be produced.

In addition, the support-integrated hydrogen separation membrane can be manufactured by performing a surface treatment process, a room temperature functional sputter process, and a low-temperature heat treatment process that are simple and highly reproducible on the porous metal support, and the composite membrane structure of dense / porous, It is possible to manufacture a support-integrated hydrogen separation membrane having improved hydrogen selectivity and permeability at the same time by forming diffusion prevention films and open interfaces together.

In addition, it is possible to produce a support-integrated hydrogen separation membrane by performing a surface treatment process, a room temperature functional sputter process and a low-temperature heat treatment process which are simple and highly reproducible, and the structural, compositional and functional properties The support membrane integrated hydrogenated membrane having improved durability in terms of thermal, chemical and mechanical stability can be manufactured by integrating the hydrogen separation membrane by exhibiting the inclined functional characteristic by progressively and continuously changing.

In addition, it is possible to produce a support-integrated hydrogen separation membrane by a room temperature functional sputtering process and a low-temperature heat treatment process without a complicated pretreatment process, and the individual processes constituting the support-integrated hydrogen separation membrane, And compatibility with each other is excellent, the reproducibility of manufacturing is excellent, so that the mass production of large area and the efficiency of the manufacturing process can be remarkably improved.

Furthermore, the above-mentioned support-integrated hydrogen separation membrane production is not limited to the type of the metal support or the palladium alloy separation layer, is widely used as a standardized manufacturing process, has excellent reproducibility in a large area and has high mass productivity, Durability, and functional characteristics, it can be widely applied to various fields such as high purity production, simultaneous reaction separation process for hydrogen separation and purification process, coal gasification combined power generation, carbon dioxide capture and storage, and the like.

Claims (17)

A surface treatment step including surface pore filling by a metal powder on a porous support and surface planarization by pressing;
Forming a hydrogen separation layer having a multi-functional dense / porous composite structure and a multi-layer structure by sputter coating at room temperature; And
Treating the porous support and the hydrogen separation layer at a low temperature of 550 DEG C or less,
Wherein the surface treatment of the porous support comprises:
A plurality of vacuum pads of the same kind of metal powders having a number of micromoles or less for selectively embedding large surface pores of several to several tens of micrometers or more existing on the surface of the porous support, Vacuum embedding nanocomposite copper or silver powders for selectively embedding pores; And
Wherein said porous support surface is planarized using a press.
The hydrogen permeation selectivity and durability of the hydrogen separation membrane are improved by forming the inclined integrated hydrogen separation membrane in which the structural, compositional, and functional properties of the porous support composed of a metal or an alloy and the hydrogen separation layer gradually and continuously change By weight of the support. delete delete The method according to claim 1,
The nanocomposite copper or silver powders buried in the surface treatment step of the porous support are subjected to a subsequent vacuum of 1.0 x 10 ^-2 torr to 760 torr and a heat treatment at a temperature of 400 ° C to 550 ° C, And forming an open interface composed of micropores by re-sintering to increase the hydrogen permeability of the hydrogen separation membrane. The method according to claim 1,
The step of forming the hydrogen separation layer may include:
The hydrogen separation membrane is formed by using a multifunctional sputter at room temperature, a high vacuum of 5.0 × 10 ^-5 torr to 5.0 × 10 ^-3 torr, and a high power process condition of 120 W to 300 W, Surface structure; And an inner porous film for maximizing the hydrogen permeability of the hydrogen separation membrane formed using a multifunctional sputtering process at room temperature, a low vacuum of 5.0 × 10 ^-3 torr to 5.0 × 10 ^-1 torr, and a low power process condition of 10 W to 100 W Structures are selectively formed,
Wherein the hydrogen selectivity and the hydrogen permeability are improved at the same time. The method according to claim 1,
The step of forming the hydrogen separation layer may include:
Silver (Ag) was sputtered at a high temperature of room temperature, a high vacuum of 5.0 × 10 ^-5 torr to 5.0 × 10 ^-3 torr, and a high power of 120 W to 300 W to form a silver coating layer of a tight- Comprising the steps of:
(Fe) or nickel (Ni), which is the main component of the porous stainless steel or nickel support, and the surface diffusion of the support components by maintaining the saturated compositions of the hydrogen separation layer at the phase separation and the compatibilizing temperature of the silver components (1). The method according to claim 1,
The step of forming the hydrogen separation layer may include:
Room temperature, 5.0 × 10 ^-5 torr to 5.0 × 10 ^-3 torr of vacuum, 120W to about 300W of power and the process conditions, and at room temperature, 5.0 × 10 ^-3 torr to 5.0 × 10 ^-1 torr for low vacuum, 10W to 100W The palladium layer and the metal layers for the alloy selected from the group consisting of silver, gold, copper, nickel, ruthenium, and yttrium are formed into multiple coating layers of a dense structure and a porous structure, respectively, Respectively,
The heat treatment at the low temperature may include:
Wherein the hydrogen permeability of the hydrogen separation membrane is maximized by maintaining a maximum permeation saturated alloy composition by performing a vacuum of 1.0 x 10 ^-2 torr to 760 torr and a low temperature heat treatment of 400 캜 to 550 캜. The method according to claim 1,
The hydrogen separation and the hydrogen permeability are simultaneously improved by forming the dense / porous composite separating layer structure, the maximum permeable saturated alloy composition, the hydrogen separation layer having the diffusion preventing function and the open interface by the room temperature sputtering step and the low temperature heat treatment step Wherein the support-integrated hydrogen separation membrane comprises a porous support. The method according to claim 1,
A standardized preliminary process composed of compatible detailed processes, and a manufacturing method that is not dependent on the type and surface state of the porous support, as well as the alloy type of the hydrogen separation layer, such as the integrated material properties of the porous support and the hydrogen separation layer , And the reproducibility and the mass productivity of the hydrogen separation membrane production are improved. The method according to claim 1,
Chemical, and mechanical properties, due to the unified characteristics of the porous support and the hydrogen separation layer, and the interfacial properties of the uniform solid solution with excellent adhesion, the inclined composition, and interconnected structures of the porous support and the hydrogen separation layer Thereby improving the durability of the support. The method according to claim 1,
Wherein the alloy of the hydrogen separation layer is at least one selected from the group consisting of palladium / silver, palladium / gold, palladium / copper, palladium / nickel, palladium / ruthenium and palladium / yttrium. The method according to claim 1,
Wherein the metal of the porous support is at least one selected from the group consisting of stainless steel, nickel, vanadium, tantalum, and titanium. The method according to claim 1,
Wherein the method for manufacturing the hydrogen separation membrane is applicable to a plate-like separation membrane of 3 inches or more or a tubular separation membrane of 10 inches or more. A porous support composed of a metal or an alloy;
A plurality of open pores are formed, and an interface formed on the porous support; And
And a hydrogen separation layer of a palladium or palladium alloy formed on the interface,
Wherein the porous support has a large surface pores of several to several tens of micrometres or more existing on the surface of the porous support and is selectively vacuum-embedded with the supports of the same kind of metal powders of several micrometers or less, Surface fine pores are selectively vacuum-filled with nano-grade copper or silver powders, surface-planarized using a press,
Wherein the structural, structural and functional properties of the porous support, the interface and the hydrogen separation layer are gradually and continuously varied and graded. 15. The method of claim 14,
And a silver (Ag) coating layer between the porous support and the hydrogen separation layer to suppress surface diffusion of the porous support metal and to maintain a maximum permeable saturated alloy composition. 16. The method of claim 15,
Wherein the maximum permeable saturated alloy composition of the hydrogen separation layer has a weight fraction of palladium: silver = 77: 23, palladium: gold = 95: 5, or palladium: copper = 60:40. 15. The method of claim 14,
Wherein the metal of the porous support is dissolved in the palladium or palladium alloy between the porous support and the hydrogen separation layer to form a uniform solid solution at the interface.

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