JP5831843B2 - Gas sorption recovery element, method for manufacturing gas sorption recovery element, and gas sorption recovery device - Google Patents

Description

  The present invention relates to a gas sorption recovery element, a method for manufacturing a gas sorption recovery element, and a gas sorption recovery apparatus. Specifically, gas sorption recovery that can efficiently sorb (absorb or adsorb) the gas generated in human waste processing, compost manufacturing process, etc., concentrate and recover, and desorb at the required concentration It relates to elements and the like.

  For example, various gases generated in human waste processing, compost manufacturing processes, and the like cause malodor. For this reason, apparatuses for recovering and processing the gas using various techniques have been proposed.

  For example, as a technique for recovering a large amount of gas at a low concentration, a sorbent having a function of sorbing the gas, for example, a honeycomb rotor in which activated carbon, zeolite or the like is supported on a honeycomb porous body, gas is supplied. In many cases, a method of once sorbing and recovering this by desorbing it with a small amount of carrier gas such as heated air and then performing a combustion treatment or the like is often employed.

JP 2001-310110 A

  In the gas sorption method described in Patent Document 1, the sorption rotor is divided into a sorption zone, a first desorption zone, and a second desorption zone in order with respect to the rotation direction, and heated by the first heater. A carrier gas such as air is passed through the first desorption zone, the carrier gas that has passed through the first desorption zone is heated again by the second heater, and is passed through the second desorption zone so that the sorption gas is desorbed from the sorbent. It is configured.

  In the above-described method, since the carrier gas such as air for collecting the sorbed gas is heated outside the sorption rotor and acts on the sorbent held in the rotor, the apparatus is large-scale. Become. Further, since the temperature of the heated carrier gas decreases while flowing inside the gas sorbent, it takes a considerable time to bring the entire sorbent to a predetermined desorption temperature. For this reason, the sorbent cannot be recovered by heating the entire sorbent to a predetermined temperature. As a result, the gas desorption efficiency is lowered. Further, in order to recover the high boiling point gas, it is necessary to heat the carrier gas twice to act on the sorbent, and the energy efficiency for desorption is low.

  On the other hand, when the sorbed gas is supplied to fuel or a fuel cell and used for power generation, it is necessary to desorb a gas having a predetermined concentration. However, the desorption rate is low, and it is difficult to obtain a desorption gas having a required concentration.

  The present invention provides a gas sorption recovery element that solves the above-mentioned conventional problems, can increase the concentration of desorbed gas, can increase the desorption rate of gas, and has high energy efficiency when desorbing. The challenge is to do.

In the present invention, a gas sorbent layer is provided on each pore surface of a porous body having continuous pores and thermal conductivity, and the gas sorbent layer is heated so as to be accommodated in the gas sorbent layer. A gas sorption / recovery element configured to desorb an attached gas, wherein the porous body includes an outer shell and a skeleton having a hollow or / and a core portion made of a conductive material, The skeleton constitutes a three-dimensional network structure in which the skeleton is continuously integrated, and part or all of it constitutes a porous heating element. The porous heating element is made of Ni or an alloy containing Ni as a main component. The predetermined portion of the formed first outer shell has a heat-generating portion alloyed with Cr, and the gas sorption recovery element is heated to at least 200 ° C. or more, whereby the gas sorbent To desorb the gas sorbed on the layer It is composed of.

  In the present invention, a gas adsorbent layer is provided on each pore surface of a porous body having continuous pores and thermal conductivity. In the porous body according to the present invention, gas can be flowed and sorbed in the continuous pores. The porous body should have a porosity of at least 90% or more, more preferably 95% or more. By adopting the porous body having the porosity, gas can be smoothly flowed and sorbed in the pores. In addition, since the porous body has thermal conductivity, the entire sorbent layer can be rapidly heated to a predetermined temperature via the porous body when the gas is desorbed. For this reason, it is possible to desorb the gas that has been sorbed in a short time, and it is possible to generate a high-concentration gas in the initial stage of desorption.

In order to improve the sorption performance, it is preferable to employ a porous body having a specific surface area of 1000 m ² / m ³ or more. By employing a material having a specific surface area equal to or larger than the above value, a large amount of sorbent can be held on the pore surface.

  Sorbents such as zeolite have the property that a large portion of the desorbable amount is desorbed at the initial stage of desorption. Further, the higher the heating temperature, the higher the concentration of the desorption gas and the higher the desorption rate. Conventionally, many are desorbed at a temperature of about 150 ° C., and the desorption time is often set to be long. During this time, since the carrier gas was allowed to flow in the pores, the concentration of the desorption gas was lowered accordingly.

  On the other hand, when the desorbed gas is used as fuel, or when the desorbed gas is supplied to the fuel cell to generate power, it is necessary to generate a desorbed gas having a predetermined concentration. In the conventional method described above, since the gas concentration at the time of desorption is low, combustion efficiency and power generation efficiency cannot be increased.

  When the sorbed gas is desorbed by heating the porous body to 200 ° C. or higher, the sorbed gas can be desorbed in a very short time and at a desorption rate higher than the conventional desorption rate. In particular, it became possible to generate a high concentration gas at the initial stage of desorption. By using the desorption gas having a high concentration at the initial stage of desorption, a gas having a required concentration can be easily generated. More preferably, the gas is desorbed by heating to 250 ° C. or higher. In addition, after heating to the above heating temperature and holding for a predetermined time, the carrier gas is flowed to recover the desorption gas, whereby a high concentration gas can be recovered. The holding time can be set according to the kind of the sorbent or gas, the required gas concentration, and the like.

  The material constituting the gas sorbent layer is not particularly limited as long as the gas sorbed at a temperature of at least 200 ° C. can be desorbed. For example, the gas sorbent layer can be formed by coating the surface of pores with a zeolite powder through a binder. Further, the thickness of the gas sorbent layer is not particularly limited as long as it does not inhibit the gas flow. For example, the thickness of the gas sorbent layer can be set to half or less of the pore diameter. Further, activated carbon, mesoporous silica or the like can be used as a sorbent.

  Moreover, it is preferable to employ a binder having a heat resistance of at least 200 ° C. as the binder for coating the sorbent. For example, a PTFE binder (polytetrafluoroethylene binder) can be employed. Furthermore, it is more preferable to employ a PTFE binder having a heat resistance of 250 ° C. or higher.

In the present invention, part or all of the porous body is composed of a porous heating element .

  By heating the porous body itself provided with the gas sorbent layer, the gas sorbent layer can be directly heated to desorb the sorbed gas. Also, the energy efficiency when desorbing the sorbed gas is very high. In addition, the entire region of the energized porous heating element can be quickly heated to a predetermined temperature. For this reason, it becomes possible to heat a gas sorbent layer to predetermined temperature in a short time, the desorption rate of gas can be raised, and a lot of gas can be desorbed by required concentration. In addition, since it is not necessary to separately provide a device for heating the carrier gas, the device can be downsized.

  Further, the gas sorbent layer can be heated to a predetermined temperature to desorb the gas without flowing the carrier gas, and then the carrier gas can be flowed. By using this method, it is possible to generate a desorption gas having an unprecedented concentration at the initial stage of desorption.

  It is not necessary that the entire porous body is a heating element, and a part of the porous body can be a heating element depending on the form of the sorption recovery element and the heating temperature.

  In order to desorb the sorbed gas in a short time, it is necessary to quickly heat the entire area of the porous body. In the case of desorption using a heated carrier gas or a configuration in which a part of the porous body is a heating element, it may be difficult to heat the entire area of the porous body to a required temperature in a short time.

On SL porous body can Rukoto provided heat conducting member formed of sheet metal. The said heat conductive member can be formed with a material with high heat conductivity, such as copper, for example. By providing the heat conducting member, the heat conductivity in the porous body is increased, and the entire area of the porous body can be rapidly heated to a temperature of 200 ° C. or higher. For this reason, a large amount of gas can be desorbed in a short time.

When the porous body is used as a heating element, if a current is supplied from a part of the porous heating element, a large current flows through the part of the porous heating element, and the porous heating element may not be heated uniformly. To avoid the above inconveniences, the porous heating element, as well as configured with a porous conductive material having a continuous pore, preferably configured to be energized through the porous conductive material.

  The porous conductor can be formed of a porous body having a resistivity lower than that of the porous heating element, such as Ni (nickel) or Cu (copper). Since the porous conductor does not generate heat at a high temperature unlike the porous heating element, wiring for power feeding can be easily connected. The resistivity of the porous conductor is preferably set to 1/100 or less of the resistivity of the porous heating element.

The porous heating element and the porous conductor can be formed from separate porous bodies and joined together by welding, caulking, or the like. Further , it is preferable that the porous heating element and the porous conductor are integrally formed from a common porous body. By adopting the above configuration, it becomes possible to make the porous structure and the porosity in the gas sorption and recovery element constant, and the flow resistance when the sorption gas is made flow in the gas sorption and recovery element. It can be made uniform. For this reason, the flowing sorption gas can be efficiently sorbed to the gas sorbent layer without hindering the flow of the sorption gas. Further, the flow of the carrier gas at the time of desorption becomes uniform, and the sorption gas can be efficiently desorbed and recovered.

The porous heat-generating body can be formed by heating the body of a predetermined region of the common porous body. There are no particular limitations on the size and number of regions and regions that form the heating element .

  For example, at least two or more porous heating elements can be provided, and the selected one or more heating elements can be energized to generate heat.

  By adopting the above configuration, it is possible to generate heat in a required portion in the gas sorption recovery element. Thereby, it becomes possible to easily adjust the desorption amount of the sorbed gas, and the amount of gas to be supplied can be adjusted in accordance with the capacity of the gas incinerator or gas decomposition apparatus provided later. Even when some of the heating elements do not generate heat due to fusing or the like, the function of the gas sorption recovery element can be maintained by supplying power to the other heating elements.

Further , the method for forming the heating element is not particularly limited. For example, the porous heating element is formed by adopting a metal porous body that can constitute the porous conductor as the common porous body, and alloying a predetermined region of the metal porous body. Can do.

  The form of the porous heating element is not particularly limited. For example, a sheet-like or plate-like porous body can be adopted. By adopting a sheet-like or plate-like porous body, a required region can be easily converted into a heating element or a conductor.

  Further, by combining two or more gas sorption / recovery elements, a gas decomposition / recovery element having a required form and size can be configured. In this case, the heating element and / or the conductor that are in contact with each other can be electrically connected. By adopting this configuration, various forms of gas sorption and recovery elements can be formed. It is also possible to configure a gas sorption / recovery element in a form that cannot be formed integrally. In particular, by stacking a plurality of sheet-like or plate-like gas sorption / recovery elements, a three-dimensional gas sorption / recovery device capable of desorbing sorbed gas by generating heat at a required portion can be easily configured. In addition, the number and form of the gas sorption / recovery elements to be combined are not particularly limited, and not only the same form of gas sorption / recovery elements but also different forms of gas sorption / recovery elements can be combined. For example, it is possible to combine gas sorption recovery elements having different porosity and gas sorption characteristics.

  In addition, by electrically connecting the porous heating element and / or the porous conductor which are in contact with each other, the heating elements and / or conductors constituting the plurality of gas sorption recovery elements are integrated, It can also function as a gas sorption recovery element. The method for electrically connecting the porous heating element and / or the porous conductor is not particularly limited. For example, the parts that contact each other can be connected and connected by welding. In addition, a connection member that allows a plurality of conductors to pass therethrough can be provided.

  Although wiring for supplying power can be directly connected to the porous conductor, it is preferable to provide an electrode portion connected to the porous conductor with a required area. For example, an electrode plate connected to the surface of the porous conductor with a required area can be provided by welding or the like, and wiring can be connected to the electrode plate. The connection area of the electrode plate can be set according to the size of the porous heating element and the porous conductor and the amount of power supplied. The material that constitutes the electrode plate is not particularly limited, and a Cu plate or the like can be adopted. Further, when combining a plurality of gas sorption and recovery elements, the electrode plates can be joined in a stretched manner on the surfaces of the plurality of conductors. It is also possible to provide a rod-shaped electrode portion that is connected through a plurality of porous conductors.

The material and form which comprise the said porous body are not specifically limited. As the porous body constituting the porous heating element and the porous conductor, for example , the common porous body includes a skeleton having an outer shell and a hollow or / and a core portion made of a conductive material. Those having a three-dimensional network structure in which the skeleton is integrally continuous can be employed.

  Since the porous body has a three-dimensional network structure, the porosity can be set extremely high. Thereby, the flow resistance of the gas in the pores is reduced, and a large amount of sorbed gas can be flowed and sorbed. Further, the skeleton is formed so as to be continuously integrated. For this reason, when a porous heating element is configured, contact resistance between adjacent fibers does not occur unlike a porous heating element configured by filling a fibrous heating element, and the porous heating element The electrical resistance in each part does not change greatly. Further, when the porous heating element and the porous conductor are made continuous in the same form, the flow resistance and electric resistance of the gas do not increase at the boundary portion. Moreover, thermal conductivity is not hindered. Therefore, the flow of the sorption gas and the carrier gas flowing in the gas sorption recovery element is not unevenly distributed. In addition, the current flowing in the porous body is not unevenly distributed, and the entire porous heating element can be uniformly heated.

Further , the three-dimensional network structure in the porous body has a plurality of branch portions constituting the skeleton gathered at a knot portion and continuously integrated, and each branch portion gathered at one knot portion. It is preferable that the outer shell has a substantially constant thickness. In particular, when a porous heating element is configured, the current from each skeleton (branch) concentrates at the above-mentioned nodule, so if the electric resistance of each branch gathered in one nodule differs, Excessive current flows through some branches, the temperature rises, and the skeleton may melt or deteriorate. By setting the thickness of the outer shells of the branches that gather at one nodule to be almost constant, there is no significant difference in the electrical resistance of each skeleton that gathers at one nodule, and it gathers at one nodal point. An excessive current does not flow through some skeletons. Thereby, it becomes possible to prevent the skeleton from being melted or deteriorated in the porous heat generating portion.

  The thickness of the outer shell of the branch portion gathering at one nodule portion of the porous heating element only needs to be substantially constant, and it is not required until the thickness of the outer shell of the entire heating element is constant. For example, depending on the manufacturing method, the thickness of the outer shell may be different between the surface layer portion of the heating element and the inside. In this case, the outer shell thickness of each branch portion gathering at the nodal portion of the surface layer portion and the outer shell thickness of the branch portion gathering at the inner nodal portion are different. However, if the thickness of the skeleton gathered at each nodule portion is substantially constant, an excessive current will not flow through some branches, and the skeleton near the nodule portion can be prevented from fusing. Moreover, since the skeleton around the nodule portion has an equal strength, the strength can be ensured.

  When the heating element is not composed of a porous body, heat conduction occurs in the skeleton portion. In this case, by adopting the skeleton having the above-described configuration, heat transfer in the porous body can be smoothly performed as in the case of current. Therefore, the entire area of the porous heating element can be heated quickly and uniformly.

The method for forming the skeleton is not particularly limited. For example , the skeleton can be formed by providing a plating layer or a metal coating layer on the surface of a three-dimensional network resin and eliminating the resin. By forming the outer shell of the skeleton from a metal plating layer or a metal coating layer, the thickness of the skeleton can be set very thin and uniform. Thereby, it becomes possible to form a porous heating element having a large porosity.

  In addition, when the outer shell is formed from a plating layer or the like, the thickness of the outer shell of the skeleton gathering at one knot portion can be formed almost constant. Thereby, a big difference does not arise in the electrical resistance and thermal resistance of the outer shell around a nodule part, and the whole region of a gas sorption recovery element can be heated uniformly.

  The said core part is comprised from a hollow or / and electroconductive material according to a manufacturing method. For example, as described above, when the skeleton is formed by providing a plating layer on the surface of a three-dimensional network resin and erasing the resin, the portion where the resin has disappeared becomes hollow. When the surface of the three-dimensional network resin is coated with a conductive material to conduct the conductive treatment in order to provide the plating layer, the surface conductive layer made of the conductive material has a hollow core portion. It may remain on the inner peripheral surface. Furthermore, when heat treatment or the like is performed after the plating treatment, the outer shell may shrink and the hollow portion may disappear. In addition, the structure of the said core part does not need to be uniform in the whole porous body, and may differ according to parts. For example, the conductive material constituting the core part may be melted by a subsequent heat treatment and unevenly distributed in the heat generating body, or a part of the hollow part may be lost.

The material constituting the outer shell having the conductivity or thermal conductivity is not particularly limited. For example, the outer shell of the porous conductor can be formed from Ni. Moreover, the material which comprises the outer shell which has exothermic property is not specifically limited, either. For example , it is preferable to form an alloy containing Ni of 50 to 95% and Cr of 5 to 50%. By setting the blending amount within the above range, the porous heating element can be efficiently heated. Other components may be blended while maintaining the blending ratio of Ni and Cr.

Said outer shell which constitutes the multi-porous heating element, a predetermined portion of the metal porous body can be configured conductive portion is a principal component of Ni, by imparting exothermic alloyed by diffusion of the Cr Can be formed. It may be difficult to form a porous body having a required porosity directly from a Ni-Cr alloy. For example, it is difficult to directly form a Ni—Cr alloy plating layer on a required portion by the above-described plating method.

In the porous heating element, first, a porous body capable of forming a porous conductor is formed from Ni, and Cr is diffused from the surface of the Ni in a predetermined region where the porous heating portion of the porous body is provided. Thus, a Ni—Cr alloy functioning as a heating element is obtained. Thereby, the exothermic part alloyed with Cr can be formed in the predetermined part of the porous body made of Ni.

  Since Ni is easily plated, the skeleton can be easily formed. Also, various metal porous bodies having different skeleton thicknesses and porosity can be easily configured. Then, by heating this Ni porous body into a Cr alloy, a heating element having required electrothermal characteristics can be configured. In addition, a predetermined region of the porous conductor constituting the porous conductor is alloyed so that the porous heating element and the porous conductor have substantially the same form and porosity. Can be formed integrally.

  The method for forming the Ni porous body into a Cr alloy is not particularly limited. For example, a Ni porous body masked in a region constituting a porous conductor is filled with Cr powder and heated, so that a portion other than the region of the Ni porous body is made into a Ni-Cr alloy. Can do. Moreover, the predetermined area | region of Ni porous body can be made into a Ni-Cr alloy by heat-processing in the mixed gas of the diffusion osmosis | permeation component gas and reducible dilution gas which were generated by heating Cr source powder.

In addition , after the second outer shell made of Cr is laminated on a predetermined portion of the first outer shell made of Ni, a predetermined heat treatment is performed, whereby the first outer shell and the first outer shell are formed. By diffusing the two outer shells to form an alloy, the outer shell constituting the porous heating element can be formed.

A method for producing a gas sorption recovery element comprising a porous heating element and a porous conductor integrally, and provided with a gas sorbent layer on at least the pore surface of the porous heating element includes the porous conductor. An alloying step for forming the porous heating element by alloying a predetermined region of the porous body that can constitute the gas, and a gas sorbent that provides a gas sorbent layer at least on the pore surface of the porous heating element It is configured to include a layer formation step.

Various gas sorption recovery devices can be configured using the gas sorption recovery element according to the present invention .

  Since the gas sorption recovery element according to the present invention can provide a gas sorbent layer on the pore surface and cause the gas to flow, the gas can be efficiently sorbed. In addition, since the outer shell is formed of a material having high thermal conductivity, the entire area of the porous body can be rapidly heated.

  Furthermore, by forming the outer shell from a heating element, the sorbent gas can be desorbed by directly heating the gas sorbent layer from the inside. Thereby, the energy required for desorption can be reduced. In addition, since the entire gas sorption / recovery element can be heated uniformly and rapidly, a gas sorption / recovery device with good gas desorption efficiency can be configured.

  Not only can the sorption gas be efficiently sorbed, but also high concentration gas can be recovered by rapidly heating the porous body to desorb the gas.

It is an electron micrograph which shows the structure of the porous body employ | adopted as this invention. It is sectional drawing which shows the structure of the porous body shown in FIG. 1 typically. It is sectional drawing which follows the II-II line in FIG. It is a graph which shows the change of the density | concentration of desorption gas with the heating temperature of a sorbent. It is a graph which shows the desorption rate by the heating temperature of a sorbent. It is a side view which shows an example of the gas sorption collection | recovery element at the time of making the said porous body into a heat generating body. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a schematic perspective view which shows an example of the gas sorption collection | recovery apparatus comprised using the porous body shown in FIG. It is sectional drawing which follows the XV-XV line | wire in FIG. It is a figure which shows the example of the gas sorption collection | recovery apparatus which concerns on 3rd Embodiment, and is sectional drawing equivalent to FIG.

  Embodiments of the present invention will be specifically described below with reference to the drawings.

  FIG. 1 is an electron micrograph showing the external structure of a porous metal body 102 constituting the gas sorption recovery element 100 according to the present embodiment. The metal porous body 102 can constitute a porous heating element depending on a material to be formed, or can constitute a porous conductor having thermal conductivity. By coating the surface of the continuous pores of the metal porous body 102 with a gas sorbent, the gas sorption recovery element 100 according to the present invention is formed.

Below, the case where the said metal porous body is used as the porous heat generating body 102 is demonstrated. The present invention is not limited to the case where the metal porous body 102 constitutes a porous heating element, and the porous body includes both the porous heating element and a metal porous body having thermal conductivity. A gas recovery sorption element can be constructed from the body .

  2 and 3 schematically show a cross-sectional structure of the gas sorption recovery element 100 configured by providing the metal porous body 102 with the gas sorbent layer 170. The metal porous body 102 has a three-dimensional network structure having continuous pores 101b. The three-dimensional network structure has a form in which triangular prism-like skeletons 110 are continuously connected in three dimensions, and a plurality of branch parts 112 constituting the skeleton 110 are aggregated into a knot part 150 and continuously integrated. Is provided. Further, as shown in FIG. 3, each part of the skeleton 110 includes an outer shell 110a and a hollow core part 110b. In the embodiment shown in FIGS. 2 and 3, in the outer shell 110a, as will be described later, the plating layer 112a and the surface conductive layer 112b are integrally alloyed to function as a heating element. It is configured.

  Since the metal porous body 102 is formed in a porous shape having continuous pores 101b, gas can flow in the pores 101b. Moreover, the porosity of the metal porous body 102 can be set extremely large by adopting a three-dimensional network structure. The porosity of the metal porous body is set to at least 90% or more, more preferably 95% or more. By employing the porous metal body 102 having the porosity, gas can be smoothly flowed and sorbed in the pores. Moreover, since the said metal porous body is formed with the metal, its heat conductivity is fundamentally high. Therefore, even when the gas is desorbed by adopting a method of heating from the outside, the entire sorbent layer can be rapidly heated to a predetermined temperature via the metal porous body. For this reason, it is possible to desorb the gas that has been sorbed in a short time, and it is possible to generate a high-concentration gas in the initial stage of desorption. Further, since the porosity is large, even if the gas sorbent layer 170 is provided, the flow resistance of the gas in the pores is low, and a large amount of gas can be flowed for sorption and desorption.

  Further, as shown in FIG. 2, the thickness t of the outer shell 110a of the branch portion 112 that gathers at one nodule portion 150 in the three-dimensional network structure is formed to be substantially constant. Since the thickness t of the outer shells of the branch portions 112 gathering at one knot portion 150 is substantially constant, the electrical resistance and thermal conductivity of each branch portion 112 gathering at one knot portion 150 are also substantially constant. Therefore, an excessive current does not flow through a part of branches gathering at one nodule, and heat conduction is not hindered. As a result, it is possible to prevent the skeleton from fusing and deterioration, and to uniformly heat the metal porous body.

  It should be noted that the thickness of the outer shell 110a of the branch portion 112 gathering at one node 150 of the metal porous body 102 only needs to be substantially constant, and the thickness of the entire outer shell of the metal porous body 102 is constant. It is not required. For example, depending on the manufacturing method or the like, it is conceivable that the thickness t of the outer shell is different between the surface layer portion and the inside of the metal porous body. In this case, the outer shell thickness of each skeleton gathering at the nodal portion of the surface layer portion is different from the outer shell thickness of the skeleton gathering at the inner nodal portion. However, if the thickness of the outer shells of the branches gathering at one nodule is almost constant, an excessive current will flow through at least some of the branches around the nodule, or it may hinder heat conduction. In addition, it is possible to prevent the skeleton in the vicinity of the nodule portion from fusing and the temperature in the metal porous body from being different depending on the part.

In order to improve the sorption performance, it is preferable to employ the porous metal body 102 having a specific surface area of 1000 m ² / m ³ or more. By adopting a specific surface area greater than the above value, a large amount of sorbent can be retained on the pore surface.

4 and 5 show that about 0.1 g of zeolite per gram is added to a strip-shaped Ni metal porous body having a porosity of 96%, a specific surface area of 1250 m ² / m ³ , and 3 × 7 × 100 mm. It shows desorption characteristics when ammonia gas is sorbed on a gas sorption recovery element formed by coating.

FIG. 4 is a graph showing the difference in the concentration of the desorbed gas recovered when N ₂ gas is allowed to flow at 50 cc / min as the carrier gas with the heating temperature varied. FIG. 4 also shows a change in concentration when a conventional PVDF binder (polyvinylidene fluoride) having low heat resistance is heated to 150 ° C. to desorb the gas. It can be seen from FIG. 4 that the concentration of the initial desorption gas increases when the heating temperature is increased. In particular, when heated to 200 ° C. or higher, the concentration of the desorbed gas can be remarkably increased as compared with the case where the PVDF binder is heated to 150 ° C., which is the use temperature.

FIG. 5 shows the desorption rate (= desorption amount / sorption amount × 100) of ammonia gas when N ₂ gas is allowed to flow at 50 cc / min as a carrier gas with different heating temperatures. From FIG. 5, it can be seen that increasing the heating temperature significantly increases the desorption rate of the gas. Further, the desorption rate of the gas after flowing 5 L of N ₂ gas is 28% when the heating temperature is 200 ° C., but increases to 41% when heated to 260 ° C. Therefore, more sorbed gas can be desorbed by increasing the heating temperature.

  In the present embodiment, as shown in the desorption characteristics, a gas having a predetermined concentration is collected using a gas having a high concentration at the initial stage of desorption. That is, a gas having a high concentration can be recovered by applying as high a temperature as possible to the gas sorption recovery element and desorbing the sorption gas in a short time.

  Since the metal porous body 102 according to this embodiment has a high porosity, it can hold a large amount of sorbent. In addition, since it has a continuous three-dimensional network structure, its thermal conductivity is uniform in the porous body. Therefore, the sorbed gas can be desorbed by heating each part of the sorbent layer 170 coated on the pore surface of the metal porous body 102 uniformly and quickly.

  The above configuration makes it possible to generate gas desorbed at a high concentration, and it is possible to increase combustion efficiency and power generation efficiency when used as fuel or when power generation is performed by a fuel cell equipped with a solid electrolyte. It becomes.

  In the present invention, the metal porous body 102 can be configured as a heating element. FIG. 6 shows a schematic structure of the gas sorption recovery element 100 when the metal porous body 102 functions as the porous heating element 102b.

  The gas sorption / recovery element 100 according to the present embodiment is formed in a porous shape having a rectangular plate shape as a whole and having continuous pores 101b.

  As shown in FIGS. 2 and 3, a gas sorbent layer 170 is provided on the surface of the continuous pore 101b. Inside the gas sorbent layer 170, a porous heating element 102b is provided at an intermediate portion in the longitudinal direction, and porous conductors 104a and 104b are provided on both sides of the porous heating element 102b. Yes. Electrode plates 103a and 103b made of conductive metal are joined to the upper surfaces of the porous conductors 104a and 104b by welding or the like. Lead wires 105a and 105b extending from the power source 106 are connected to the electrode plates 103a and 103b, and the electrode plates 103a and 103b and the porous heating element 102 provided inside the gas sorption and recovery element 100 are connected to the electrode plates 103a and 103b. It is configured to be able to generate heat by supplying power through the porous conductors 104a and 104b. In addition, it can also comprise so that a lead wire may be directly connected to a porous heat generating body and it may supply electric power.

  Since the porous heating element 102b and the porous conductors 104a and 104b are formed of porous bodies having substantially the same form and porosity as shown in FIGS. 1 to 3, the gas flow resistance is also substantially the same. . A gas can be caused to flow in a gas adsorption / recovery element in which a gas adsorbent layer is provided on the pore surface of the porous body, so that the gas can be efficiently sorbed onto the gas sorbent layer.

  The porous heating element 102b according to the present embodiment is formed from an alloy containing at least Ni and Cr. The blending amount of Ni and Cr can be set according to the required calorific value. For example, the outer shell 110a of the porous heating element 102b can be formed of an alloy containing 50 to 95% Ni and 5 to 50% Cr.

  The porous heating element 102b can be formed using various methods. For example, by forming a metal porous body that can constitute the porous conductors 104a and 104b having the structure described above, and by forming a predetermined region (region corresponding to the heating element) of the metal porous body into a Cr alloy. Through the alloying step of forming the porous heating element 102b, a metal porous body in which the porous heating element 102b and the porous conductor are integrated can be formed.

  When the skeleton constituting the porous heating element 102b is formed by plating, a step of conducting a conductive treatment on the three-dimensional network resin, a step of applying Ni plating to the three-dimensional network resin, and the region other than the region to be alloyed A masking step in which a masking layer for plating or coating treatment is provided in the region, a layering step in which a metal such as Cr is plated or coated in a region not subjected to the masking, and a step of removing the three-dimensional network resin And a heat treatment step of heating the porous body to which the plating or coating is applied and alloying the stacked Ni layer and Cr layer.

  As a form of the three-dimensional network resin, a resin foam, a nonwoven fabric, a felt, a woven fabric, or the like can be used. Although the raw material which comprises the said three-dimensional network resin is not specifically limited, It is preferable to employ | adopt what can be lose | disappeared by heating etc. after metal-plating. Moreover, in order to ensure workability and handling property, it is preferable to employ a flexible one. In particular, it is preferable to employ a resin foam as the three-dimensional network resin. The resin foam may be a porous material having continuous pores, and a known one can be adopted. For example, a foamed urethane resin, a foamed styrene resin, or the like can be used. There are no particular limitations on the pore shape, porosity, dimensions, and the like of the foamed resin, and they can be set as appropriate according to the application.

  The treatment for making the three-dimensional network resin conductive is performed in order to provide the metal plating layer constituting the skeleton on the surface of each pore, and particularly if the surface conductive layer 112b in FIG. 3 can be provided. There is no limit. For example, when nickel is used, an electroless plating process, a sputtering process, or the like can be employed. In addition, when adopting metals such as titanium and stainless steel, carbon black, graphite, etc., it is possible to employ a treatment of impregnating and applying the mixture obtained by adding a binder to these fine powders to the three-dimensional network resin. it can.

  The plating treatment is not particularly limited, and the treatment can be performed by a known plating method. For example, in the case of nickel plating, it is preferable to employ an electroplating method from the viewpoint of productivity, cost, and the like. A well-known or commercially available thing can be employ | adopted as a plating bath used for electroplating.

The thickness (weight per unit area) of the Ni plating layer is not particularly limited. It can be set in consideration of the required porosity and strength. For example, it is possible to employ a unit weight of ^{100g / m 2 ~2000g / m 2} .

By the above method, first, a Ni plating layer is formed, masking is performed on a region constituting the conductor, and then a Cr plating layer is laminated. The thickness of the Cr plating layer (basis weight) also is not particularly limited, for example, can be set in a range of ^{10g / m 2 ~1000g / m 2} .

  After the plating layer is formed, a step of removing the three-dimensional network resin is performed. The step of removing the three-dimensional network resin may be performed by, for example, heat-treating the porous body provided with the plating layer at 600 ° C. to 800 ° C. in an oxidizing atmosphere such as air in a stainless muffle. Dimensional network resin can be removed by incineration.

Further, the Cr plating is performed by heat-treating the porous body in which the Cr plating layer is formed on the Ni plating layer in a stainless muffle in a reducing gas atmosphere such as CO or H 2 at 800 ° C. to 1000 ° C. The Ni—Cr alloy layer can be formed by diffusing the layer and the Ni plating layer. Further, in an inert gas atmosphere such as N ₂ or Ar, an alloy layer can be formed from the Cr plating layer and the Ni plating layer by heating to 1000 ° C. to 1500 ° C. in a carbon muffle. In the case where the surface conductive layer 112b shown in FIGS. 3 and 4 is provided by Ni, the surface conductive layer 112b is also Ni—Cr alloyed in the alloying step, and the whole becomes a heating element.

  By adopting the above process, it is possible to form a porous heating element with little variation in chromium concentration in the outer shell, high corrosion resistance and high heat generation characteristics. Further, since the outer shell is constituted by the plating layer, the thickness (cross-sectional area) of the outer shell can be set almost uniformly in the porous body. For this reason, the dispersion | variation in the electrical resistance in a porous body decreases, and the whole porous body can be heated uniformly by supplying with electricity.

  As shown in FIG.2 and FIG.3, although the said core part 110b which concerns on this embodiment is formed in hollow shape, it is not limited to this. That is, in the above-described embodiment, the surface conductive layer 112b formed of Ni is integrated with the outer shell because it is Cr alloyed. However, when the surface conductive layer is formed of another conductive material, the core It may remain as a part. For example, when the surface conductive layer is formed from titanium, carbon, or the like, and the skeleton is formed by Ni plating and then Cr alloyed, the surface conductive layer remains as a core without being alloyed. . Further, in the heat treatment step of forming the Ni plating layer into a Cr alloy, the outer shell may shrink and the hollow core portion may disappear. In addition, the thickness etc. of the said surface conductive layer are set so that the required heat generation performance of a porous heat generating body may not be inhibited.

  A gas sorbent is coated on the surface of the continuous pores of the porous body integrally formed with the porous heating element 102b and the porous conductors 104a and 104b formed as described above. Adhesive layer 170 is formed.

  The method for forming the gas sorbent layer 170 is not particularly limited, and can be formed using various methods. For example, the gas sorbent layer 170 can be formed by applying a paste formed by mixing zeolite powder, a binder, and a solvent to the porous body and drying the paste. The binder is preferably formed from the above-described PTFE resin having high heat resistance and can be heated at a temperature of at least 200 ° C.

  The thickness of the gas sorbent layer 170 is not particularly limited. In the case of this embodiment, the gas sorbent layer 170 is formed with a thickness of 100 μm. However, if the porosity that does not inhibit the flow of gas can be secured, the gas sorbent layer 170 can be formed with a large thickness to increase the sorption capacity. For example, the thickness of the gas sorbent layer 170 is preferably set to half or less of the pore diameter. Moreover, it is preferable that the porosity after forming the gas sorbent layer 170 is 26% to 32%. The method for forming the gas sorbent layer is not particularly limited. It can be formed using other techniques.

  The gas sorption / recovery element 100 shown in FIG. 6 can be specifically formed by the technique shown in FIGS. 7 to 14 schematically show a method for manufacturing the gas sorption recovery element 100. In these drawings, a part of the manufacturing process of the gas sorption recovery element in FIG. 6 is shown.

  First, in order to form a common skeleton constituting the porous conductors 104a and 104b and the porous heating element 102b shown in FIG. 6, a three-dimensional network resin 160 shown in FIG. 7 is prepared. The three-dimensional network resin 160 includes a portion 160a corresponding to the hollow core portion constituting the skeleton and a continuous pore portion 160b corresponding to continuous pores. For example, the three-dimensional network resin 160 can be formed by foaming urethane resin with a predetermined porosity.

As shown in FIG. 8, the surface of the three-dimensional mesh resin 160 is subjected to a conductive treatment by the above-described method, and then a Ni plating layer 111 is formed on the entire surface. The Ni plating layer 111, which constitutes the porous conductive material 104a, 104b in FIG. 6, as described above, can be formed by unit weight of ^{100g / m 2 ~2000g / m 2} . Thereafter, as shown in FIG. 9, a masking layer 122 for the Cr plating treatment is formed on a portion constituting the porous conductor 104 b. The masking layer 122 can be formed of, for example, an epoxy resin.

  Next, as shown in FIG. 10, a Cr plating layer 113 is provided on the porous body provided with the masking layer 122 by the above-described method. Since the masking layer 122 is provided, the Cr plating layer 113 can be formed only in a region corresponding to the porous heating element 102. As a result, a composite plating layer 120 in which the Ni plating layer 111 and the Cr plating layer 113 are laminated is formed in the portion constituting the porous heating element 102b.

  As shown in FIG. 11, the masking layer 122 is removed after the composite plating layer 120 is formed. Thereafter, the above-described process of removing the three-dimensional network resin is performed. As shown in FIG. 12, only the Ni plating layer 111 is provided to form the conductor 104b, and the Ni plating layer 111 has a Cr plating layer. A three-dimensional mesh-like metal porous body 114 is formed in which a region including the composite plating layer 120 on which 113 is laminated is integrally continuous.

  The metal porous body 114 is heat-treated at 800 ° C. to 1000 ° C. in a reducing gas atmosphere such as CO and H 2 in a stainless steel muffle, whereby the Ni plating layer 111 constituting the composite plating layer 120 and The Cr plating layer 113 is diffused to form a Ni—Cr alloy, and the porous heating element 102 is formed. As shown in FIG. 13, the metal porous body 114 is composed of a skeleton 101 of a porous heating element 102b composed of a hollow core portion 101c and a Cr alloyed outer shell 101a, a hollow core portion 111c and Ni alone. The skeleton 121 of the conductor 104b including the formed outer shell 111a is continuously formed.

  By adopting the above method, a required part of the metal porous body formed of Ni is Ni—Cr alloyed, and the porous heating element 102 and the Cr alloy continuous with the porous heating element 102 are formed. The porous conductor 104b that is not present can be formed integrally. Since the gas sorbent layer 170 is often formed of an insulating material, the electrode plate 103b is provided on the upper surface of the porous conductor 104b before the gas sorbent layer 170 is formed.

  Zeolite powder, binder (PTFE 60% dispersion) and solvent (CMC 0.5% aqueous solution) are mixed in a weight ratio of 12 g: 3.1 g: 32.5 g over the entire area excluding the electrode of the metal porous body 114 having the above-described configuration. A paste formed by mixing is applied, and the solvent is removed by heating to form the gas sorption recovery element 100 shown in FIG.

  FIG. 15 shows an example in which the gas sorption recovery device 200 is formed using the gas sorption recovery element formed by the above-described method.

  The gas sorption and recovery apparatus 200 according to the present embodiment divides a cylindrical rotor 201 into four regions A, B, C, and D by electrically insulating partition walls 202a, 202b, 202c, and 202d that extend in the radial direction. The gas sorption / recovery elements 207a, 207b, 207c, and 207d are arranged in this section.

The rotor 201 is rotated by a motor (not shown) to cause a sorbed gas to flow in a region at a predetermined rotational position and sorb to the gas sorbent layer, while the porous heat generation at the predetermined rotational position. The body is energized and heated, and the above-described carrier gas such as N _{2 is made} to flow so that the gas absorbed in the sorbent layer can be desorbed and recovered.

  As shown in FIG. 16, in this embodiment, the gas sorption / recovery elements 207a, 207b, 207c, and 207d arranged in the respective regions A, B, C, and D are held on the rotating shaft 212 at the inner peripheral portion. Cylindrical wall-shaped first electrode plates 213a, 213b, 213c, 213d, cylindrical wall-shaped second electrode plates 214a, 214b, 214c, 214d provided so as to cover the outer periphery, and between these electrode plates A porous sorption part 211a, 211b, 211c, 211d provided in the space is provided. Although not shown, each of the porous sorption portions 211a, 211b, 211c, and 211d is formed by coating a gas sorbent on an integrally formed porous heating element and porous conductor.

  The current from the power source 220 is supplied to the first electrode plates 213a, 213b, 213c, and 213d provided on the outer periphery of the rotating shaft 212 of the rotor 201, the second electrode plates 214a, 214b, 214c, and 214d while rotating. The gas sorption / recovery elements 207a, 207b, 207c, and 207d are sequentially flowed through a current-carrying member 215 brought into contact with the electrode plate. As a result, the gas sorption / recovery elements 207a, 207b, 207c, and 207d are sequentially heated, and the gas sorbed on each gas sorbent layer is desorbed and recovered together with the carrier gas.

  When ammonia gas having a concentration of 200 ppm was ventilated at a flow rate of 8 cm / sec through the gas sorption recovery apparatus 200 having the above configuration, the ammonia gas concentration after sorption became 1 to 2 ppm.

On the other hand, when the gas sorption recovery element in the region where the ammonia gas was sorbed was energized and heated to 200 to 260 ° C. and N ₂ was flowed as the carrier gas, ammonia having a concentration of 4400 ppm was detected at the initial stage of desorption. did.

  By adopting the above configuration, the generated gas can be continuously sorbed and recovered. Further, in the gas sorption recovery apparatus having the above-described configuration, the heating temperature and the above-described temperature are set so that the desorption region is heated to a predetermined temperature and then held for a predetermined time to desorb the gas into the porous body, and then cause the carrier gas to flow. The rotation of the rotor 201 can be controlled. By adopting this method, it is possible to continuously recover a gas having a high concentration at the initial stage of desorption.

  FIG. 17 shows a third embodiment of the present invention. In this embodiment, the metal porous body coated with a gas sorbent is not used as a heating element, but the present invention is applied to the case where the sorption gas is desorbed by external heating or heating and flowing the carrier gas. It is a thing.

  In order to desorb the gas from the gas sorption recovery element in a short time using external heating, it is necessary to heat the gas sorption recovery element to a predetermined temperature in a short time. On the other hand, in a large gas sorption recovery apparatus as shown in FIG. 15, it takes a considerable time to heat the entire gas sorption recovery element to a predetermined temperature. For this reason, it is difficult to desorb the sorption gas in a short time.

  In the present embodiment, a heat conduction member 314a is provided inside the gas sorption recovery elements 207a to 207d in FIG. The heat conducting member 314a is made of a plate metal having high heat conductivity, and is arranged in a direction along the gas flow direction so as not to hinder the gas flow.

  By providing the heat conducting member 314a, the thermal conductivity in each gas adsorption / recovery element is remarkably increased, and it is possible to prevent a temperature difference from occurring in each part of the gas adsorption / recovery element.

  In addition, it becomes possible to quickly conduct the heat acting from the external heating or the carrier gas to the metal porous body through the heat conducting member, and the gas sorption recovery element is quickly heated to a predetermined temperature to be collected. The attached gas can be desorbed in a short time.

  The present invention can be applied to gases generated in various processes. Further, the scope of the present invention is not limited to the above-described embodiment. The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined not by the above-mentioned meaning but by the scope of the claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims.

  A large amount of gas can be sorbed, and high concentration gas can be efficiently desorbed and recovered.

100 Gas Sorptive Recovery Element 101b Continuous Pore 102 Porous Body 102b Porous Heating Element 170 Gas Sorbent Layer

Claims (10)

A gas sorbent layer is provided on each pore surface of a porous body having continuous pores and thermal conductivity, and the gas sorbent layer is heated to heat the gas sorbed to the gas sorbent layer. A gas sorption recovery element configured to desorb
The porous body includes a skeleton having an outer shell and a core portion made of a hollow or / and conductive material, and constitutes a three-dimensional network structure in which the skeleton is integrally continuous. All of them constitute a porous heating element,
The porous heating element has a heat-generating part alloyed with Cr in a predetermined part of the first outer shell formed of Ni or an alloy containing Ni as a main component,
The gas sorption recovery device, by heating to at least 200 ° C. or higher, and is configured to desorb the sorbed gas to the gas sorbent layer, gas sorption recovery device.
The gas sorption / recovery element according to claim 1, wherein a heat conducting member made of a plate-like metal is provided in the porous body. 3. The porous heating element according to claim 1 or 2, wherein the porous heating element is configured to include a porous conductor having continuous pores and can be energized through the porous conductor. Gas sorption recovery element. The gas sorption recovery element according to any one of claims 1 to 3 , wherein the porous heating element and the porous conductor are integrally formed from a common porous body. The gas sorbent layer is formed by coating zeolite powder on the pore surface of the porous body through a binder,
The gas sorption recovery element according to any one of claims 1 to 4 , wherein the binder has a heat resistance of at least 200 ° C or higher. In the three-dimensional network structure, a plurality of branches constituting the skeleton gather together at a knot and are integrally continuous, and the thickness of the outer shell of each branch gathered at one knot is substantially equal. The gas sorption recovery element according to any one of claims 1 to 5 , which is constant. Said skeleton is composed of a plating layer or a metal coating layer, the gas sorption recovery device as claimed in any one of claims 1 to 6.
The shell constituting the porous heating element, and from 50% to 95% of Ni, it is formed a Cr alloy containing 5 to 50% claimed in any one of claims 7 Gas sorption recovery element. A method for producing a gas sorption recovery element according to claim 1 ,
By alloying the predetermined region of the porous body can be configured multiple Anashitsushirube collector, the alloying step of forming the porous heating element,
And a gas sorbent layer forming step of providing a gas sorbent layer on the pore surface of the porous heating element. A gas sorption recovery apparatus comprising the gas sorption recovery element according to any one of claims 1 to 9 .

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