JP2013010090A - Gas sorption recovery element, method of manufacturing gas sorption recovery element, and gas sorption recovery apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas sorption recovery apparatus which can reliably detach and recover a gas sorbed on a gas sorbent, has high energy efficiency upon recovery, and is applicable in various gas treatment apparatuses.SOLUTION: A gas sorption recovery element 100 is configured such that a gas sorbent layer 170 is provided for each pored surface of a porous heating element 102 having a continuous pore 101b, and the porous heating element is energized and heated so that the gas sorbed on the gas sorbent layer is detached.

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. More specifically, the present invention relates to a gas sorption / recovery element or the like that can efficiently sorb (absorb or adsorb) gas generated in human waste processing or compost manufacturing process, and concentrate and recover the gas.

  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. In addition, since the temperature of the heated carrier gas decreases while flowing inside the gas sorbent, it is impossible to recover the sorbed gas by heating the entire sorbent to a predetermined temperature. For this reason, the recovery efficiency of gas becomes low. 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 is low.

  On the other hand, in many cases, a method of incineration of the sorbent without recovering the sorbed gas is employed, but the running cost increases.

  The present invention solves the above-described conventional problems, and provides a gas sorption recovery element that can reliably desorb and recover the gas sorbed by the sorbent and has high energy efficiency when recovered. It is said.

  The invention described in claim 1 of the present application provides a gas sorbent layer on each pore surface of a porous heating element having continuous pores, and energizes the porous heating element to generate heat to thereby generate the gas sorption. The present invention relates to a gas sorption recovery element configured to desorb a gas sorbed on an agent layer.

  In the gas sorption recovery element according to the present invention, since the gas sorbent layer and the heating element are integrally formed, the gas sorbent layer can be directly heated to desorb the sorbed gas. it can. For this reason, the energy efficiency when desorbing the sorbed gas is extremely high. In addition, the entire area of the energized porous heating element can be rapidly heated to a predetermined temperature. For this reason, not only the gas desorption efficiency is high, but also a large amount of gas can be sorbed and desorbed. In addition, since it is not necessary to separately provide a device for heating the carrier gas, the device can be miniaturized.

  The material constituting the gas sorbent layer and the forming method are not particularly limited. It can be selected according to the type of adsorbed gas. 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.

  When energizing from a part of the porous heating element, a large current flows through a part of the porous heating element, and there is a possibility that the porous heating element cannot be heated uniformly. In order to avoid the inconvenience, as in the invention described in claim 2, the porous heating element includes a porous conductor having continuous pores, and the porous conductor is interposed through the porous conductor. It is preferable to configure so that it can be energized.

  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, as in the invention described in claim 3, 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.

  At least one of the porous heating element and the porous conductor can be formed by converting a predetermined region of the common porous body into a heating element or a conductor. There are no particular limitations on the size and number of the regions and regions that become the heating element or the conductor.

  For example, as in the invention described in claim 4, 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, there is no particular limitation on the method for forming a heating element or a conductor. 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.

  In addition, a metal porous body that can constitute the porous heating element is adopted as the common porous body, and the porous conductor is formed by providing a conductive layer on the surface of a predetermined region of the metal porous body. can do. The conductive layer can be formed, for example, by coating a conductive material such as metal on a region constituting the porous conductor. Furthermore, the porous heating element and the porous conductor may be formed by continuously forming both the exothermic region and the conductive region on the insulating porous body. it can.

  The form of the porous heating element is not particularly limited. For example, a sheet-like or plate-like porous heating element can be employed. 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, an electrode portion connected to the porous conductor with a required area is provided as in the invention described in claim 6. preferable. 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 heat generating body and the said porous conductor are not specifically limited. As the porous body constituting the porous heating element and the porous conductor, for example, as in the invention described in claim 7, the common porous body imparts heat generation or conductivity to a predetermined region. It is possible to employ a structure having a skeleton having a formed outer shell and a hollow or / and a core portion made of a conductive material, and constituting a three-dimensional network structure in which the skeleton is integrally continuous.

  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. Therefore, unlike a porous heating element configured by filling a fibrous heating element, contact resistance between adjacent fibers does not occur, and the electrical resistance in each part of the porous heating element changes greatly. There is no. Further, since the porous heating element and the porous conductor are continuous in the same form, the flow resistance and electric resistance of the gas do not increase at the boundary portion. 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, as in the invention described in claim 8, the three-dimensional network structure in the porous body has a plurality of branch portions constituting the skeleton gathered at a knot portion and integrally continuous. It is preferable that the thickness of the outer shell of each of the branch portions gathered at one nodule portion is substantially constant. Since the current from each skeleton (branch part) concentrates in the above-mentioned nodal part, if the electric resistance of each branch part gathering in one nodule part is different, an excessive current flows in some of the branch parts around the nodule part. As a result, 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.

  The method for forming the skeleton is not particularly limited. For example, as in the invention described in claim 9, 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 of the outer shell around the knot, and the entire region of the 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. 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.

  The material constituting the outer shell having 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, as in the invention described in claim 10, 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.

  As in the invention described in claim 11, the exothermic outer shell is alloyed by diffusing Cr into a predetermined portion of a porous metal body that has Ni as a main component and can constitute a conductive portion. It can be formed by imparting exothermic properties. 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.

  According to the eleventh aspect of the present invention, first, a porous body capable of forming a porous conductor is formed from Ni, and Cr is formed from a surface of the Ni in a predetermined region where the porous heat generating portion of the porous body is provided. Ni—Cr alloy functioning as a heating element is diffused.

  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.

  Further, as in the invention described in claim 12, after a 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. Thus, the first outer shell and the second outer shell are diffused and alloyed with each other, thereby forming an outer shell imparted with heat generation.

  The invention described in claim 13 is a gas sorption recovery element comprising a porous heating element and a porous conductor integrally, and at least a gas sorbent layer provided on the pore surface of the porous heating element. An alloying step for forming the porous heating element by alloying a predetermined region of the porous body that can constitute the porous conductor, and at least a pore surface of the porous heating element. And a gas sorbent layer forming step of providing a gas sorbent layer.

  The invention described in claim 14 is a gas sorption recovery element comprising a porous heating element and a porous conductor integrally, and at least a gas sorbent layer provided on the pore surface of the porous heating element. A method of manufacturing, wherein a conductive layer is provided on a surface of a predetermined region of the porous heating element that can constitute the porous heating element, thereby forming the porous conductor, and at least the porous heating element A gas sorbent layer forming step of providing a gas sorbent layer on the pore surface of the body.

  The invention described in claim 15 relates to a gas sorption recovery apparatus including the gas sorption recovery element described in claims 1 to 12.

  The gas sorption / recovery element according to the present invention can sorb gas efficiently because a gas sorbent layer can be provided on the pore surface of the porous heating element that generates heat by itself to flow the gas. It becomes. Moreover, since the sorbed gas can be desorbed by directly heating the gas sorbent layer from the inside, the energy required for desorption can be reduced. In addition, since the entire gas sorption / recovery element can be heated uniformly, a gas sorption / recovery device with good gas desorption efficiency can be configured.

  Not only can the sorbed gas be efficiently sorbed, but also the gas sorbent layer can be heated directly, so that the sorbed gas can be efficiently desorbed and a large amount of gas can be efficiently absorbed. Can be put on and taken off.

It is a side view which shows typically the structure of the gas sorption collection | recovery element which concerns on 1st Embodiment of this invention. It is an electron micrograph which shows an example of the porous body which comprises a porous heat generating body and a porous conductor. It is a figure which shows typically the cross section of the principal part of the gas sorption collection | recovery element formed from the porous body shown in FIG. It is sectional drawing which follows the IV-IV line 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 figure which shows the manufacturing process of the gas sorption collection | recovery element shown in FIG. It is a schematic perspective view of the gas sorption collection | recovery apparatus which concerns on 2nd Embodiment. It is sectional drawing which follows the XIV-XIV line | wire in FIG. It is a system diagram of the gas sorption collection | recovery apparatus which concerns on 3rd Embodiment. It is sectional drawing of the gas sorption collection | recovery element which concerns on 4th Embodiment.

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

  FIG. 1 is a side view schematically showing a schematic configuration of a gas sorption recovery element 100 according to a first embodiment of the present invention. As shown in FIG. 1, the gas sorption recovery element 100 is formed in a porous shape having an outer shape formed in a rectangular plate shape and having continuous pores 101 b as a whole.

  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 102 is provided at an intermediate portion, and porous conductors 104a and 104b are provided on both sides of the porous heating element 102. 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 102 and the porous conductors 104a and 104b are formed of porous bodies having substantially the same form and porosity, 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.

  FIG. 2 is an electron micrograph showing an external structure of an example of a metal porous body constituting the porous heating element 102 and the porous conductors 104a and 104b. As described later, in the present embodiment, the porous heating element 102 described above is formed by alloying an intermediate portion of the Ni porous body that can form the porous conductors 104a and 104b. The gas sorbent layer 170 is formed by coating the continuous pore surfaces of the porous heating element 102 and the porous conductors 104a and 104b with a gas sorbent. Since the porous conductors 104a and 104b and the porous heating element 102 have substantially the same porous structure, the following description will be made on the porous heating element 102.

  3 and 4 show a cross-sectional structure of the gas sorption recovery element 100 in which the gas sorbent layer 170 is provided on the porous heating element 102 and the porous conductors 104a and 104b. The porous heating element 102 has a three-dimensional network structure having continuous pores 101b. As shown in FIG. 3, the three-dimensional network structure has a configuration in which triangular prism-like skeletons 110 are continuously connected in three dimensions, and a plurality of branches 112 constituting the skeleton 110 are gathered at a nodule 150. In a single continuous form. Further, as shown in FIG. 4, each part of the skeleton 110 includes an outer shell 110a and a hollow core part 110b. In the embodiment shown in FIGS. 3 and 4, 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 porous heating element 102 is formed in a porous shape having continuous pores 101b, gas can flow in the pores 101b. In addition, the porous heating element 102 can have a very high porosity by adopting a three-dimensional network structure. For this reason, 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 and sorbed.

  Further, as shown in FIG. 3, 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 of each branch portion 112 gathering at one knot portion 150 is also substantially constant. Therefore, an excessive current does not flow through some branches gathered in one nodule. Thereby, it becomes possible to prevent fusing and deterioration of the skeleton.

  It should be noted that the thickness of the outer shell 110a of the branch portion 112 gathering at one node 150 of the porous heating element 102 only needs to be substantially constant, and the thickness of the outer shell of the entire heating element is required to be constant. It is not a thing. For example, depending on the manufacturing method or the like, it is conceivable that the thickness t of the outer shell differs between the surface layer portion and the inside of the heating element. 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 not flow at least to some branches around the nodule, and the skeleton near the nodule Fusing can be prevented.

  The porous heating element 102 according to this embodiment is formed of 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 102 can be formed of an alloy containing 50 to 95% Ni and 5 to 50% Cr.

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

  When the skeleton constituting the porous heating element 102 is formed by plating, the step of conducting a conductive treatment on the three-dimensional network resin, the 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.

Furthermore, the above-mentioned Cr body is heat-treated at 800 ° C. to 1000 ° C. under a reducing gas atmosphere such as CO or H ₂ in a stainless muffle with a porous body in which a Cr plating layer is formed on the Ni plating layer. The Ni—Cr alloy layer can be formed by diffusing the plating layer and the Ni plating layer with each other. 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.3 and FIG.4, although the said core part 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 in which the porous heating element 102 and the porous conductors 104a and 104b, which are formed as described above, are integrally formed. 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 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. 1 can be specifically formed by the technique shown in FIGS. 5 to 12 schematically show a method for manufacturing the gas sorption recovery element 100. FIG. In these drawings, a part of the manufacturing process of the gas sorption recovery element in FIG. 1 is shown.

  First, in order to form a common skeleton constituting the porous conductors 104a and 104b and the porous heating element 102 shown in FIG. 1, a three-dimensional network resin 160 shown in FIG. 5 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. 6, 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. 1, as described above, can be formed by unit weight of ^{100g / m 2 ~2000g / m 2} . Thereafter, as shown in FIG. 7, a masking layer 122 for the Cr plating treatment is formed on the 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. 8, a Cr plating layer 113 is provided on the porous body provided with the masking layer 122 by the method described above. 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 on the portion constituting the porous heating element 102.

  As shown in FIG. 9, 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, and as shown in FIG. 10, 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. 11, the metal porous body 114 is composed of a skeleton 101 of a porous heating element 102 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.

  A paste formed by mixing zeolite powder, binder (PVdF12% NMP) and solvent (NMP) at a weight ratio of 3: 4: 5 is applied to the entire area excluding the electrode of the metal porous body 114 having the above configuration. Then, the solvent is removed by heating to form the gas sorption recovery element 100 shown in FIG.

  FIG. 13 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 carrier gas is made to flow so that the gas sorbed on the sorbent layer can be desorbed and recovered.

  As shown in FIG. 14, in this embodiment, the gas sorption recovery elements 207 a, 207 b, 207 c, and 207 d 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 100 to 150 ° C., and N 2 was flowed as the carrier gas, ammonia having a concentration of 1500 ppm was detected.

  By adopting the above configuration, the generated gas can be continuously sorbed and recovered.

  FIG. 15 shows a gas sorption recovery apparatus 300 according to the third embodiment of the present invention. In this embodiment as well, the basic configuration of the porous sorbent body, the porous heating element, and the gas sorption recovery element is the same as that of the first embodiment, and the description thereof will be omitted.

  In the third embodiment, a plurality of cylindrical containers 301a, 301b, 301c are filled with gas sorption recovery elements 307a, 307b, 307c, respectively, and these containers are connected by piping connected to two sets of switching valves. Thus, a gas sorption recovery apparatus 300 is configured.

  Each cylindrical container 301a, 301b, 301c is provided with a sorption gas inlet 303a through which sorption gas flows and a discharge port 303b through which the remaining gas after sorption is discharged. A pipe extending from the first four-way valve 351 and a pipe extending from the second four-way valve 352 are connected to the sorption gas inlet 303a of each of the cylindrical containers 301a, 301b, 301c. By switching between the first four-way valve 351 and the second four-way valve 352, the sorption gas can be sequentially flowed into each cylindrical container for sorption, and the remaining gas after sorption It can be discharged.

  Each cylindrical container 301a, 301b, 301c is provided with a carrier gas inlet 304a through which carrier gas flows in and a recovery port 304b through which the desorbed desorbed gas and carrier gas are collected. A pipe extending from the third four-way valve 353 is connected to the carrier gas inlet 304a of each cylindrical container, and a pipe extending from the fourth four-way valve 354 is connected to the recovery port 304b. It is connected. By switching the third four-way valve 353 and the fourth four-way valve 354, the carrier gas can be sequentially introduced into each cylindrical container, and the desorbed gas can be recovered. .

  The gas sorption and recovery elements 307a, 307b, and 307c are formed of a porous body having a cylindrical shape corresponding to a cylindrical container, and the first electrode portion 311 and the second electrode portion are provided on the outer peripheral portion of the axial end edge. The electrode portions 312 are respectively provided. The first electrode portion 311 and the second electrode portion 312 are respectively connected to a power source 306 through lead wires. Each of the four-way valves is controlled to flow a carrier gas into a gas recovery container, and the energized gas sorption recovery element is energized so that the gas sorbed in the gas sorption recovery element is reduced. It can be desorbed and recovered with the carrier gas.

  By adopting the above configuration, the sorbed gas can be continuously sorbed and continuously desorbed and recovered.

  FIG. 16 shows a fourth embodiment of the present invention. In the fourth embodiment, a plurality of porous heating elements 402a, 402b, and 402c and porous conductors 404a, 404b, and 404c that are alternately provided so as to sandwich the plurality of porous heating elements 402a, 402b, and 402c. , 404d is provided with a gas sorbent layer on the surface of the porous body 410 to constitute the gas sorption recovery element 400. In FIG. 16, the gas sorbent layer is not shown for easy understanding, but the gas sorbent layer is provided over the entire surface. Note that the basic configuration of each part of the gas sorption recovery element is the same as that of the above-described embodiment, and a description thereof will be omitted.

  The gas sorption element 400 according to the fourth embodiment has a form in which porous conductors 404a, 404b, 404c, 404d and porous heating elements 402a, 402b, 402c are alternately formed in the gas flow direction. Prepare. Moreover, the said porous conductor and the said porous heat generating body are formed from the porous body provided with the same frame | skeleton.

  Electrode plates 403a, 403b, 403c, and 403d made of conductive metal are joined to the upper surfaces of the respective porous conductors 404a, 404b, 404c, and 404d by welding or the like.

  Wiring lines 405a, 405b, 405c, and 405d extending from the power source 406 are connected to the electrode plates 403a, 403b, 403c, and 403d, and the electrode plates 403a, 403b, 403c, and 403d, the porous conductors 404a, Power is supplied to the porous heating elements 402a, 402b, and 402c through 404b, 404c, and 404d.

  In this embodiment, a wiring 405 a extending from the electrode plate 403 a provided on the porous conductor 404 a at the left end is connected to one electrode of the power source 406. On the other hand, wirings 405b, 405c, 405d extending from the electrode plates 403b, 403c, 403d provided on the other porous conductors 404b, 404c, 404d are selectively connected to the wiring 406a extending from the other electrode of the power source 406. It is configured to be able to.

  By adopting the above configuration, it is possible to generate heat by supplying power to the porous heating element in a desired range from the porous heating element 402a at the left end. For this reason, it becomes possible to selectively desorb the gas sorbed to the gas sorbent layer in the heated portion. As a result, gas can be desorbed and processed according to the capability of the gas processing apparatus or the like.

  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 can be efficiently desorbed and recovered.

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

Claims (15)

  A gas sorbent layer is provided on each pore surface of the porous heating element having continuous pores, and the gas sorbed in the gas sorbent layer is desorbed by energizing the porous heating element to generate heat. A gas sorption recovery element configured as described above.   The gas sorption recovery according to claim 1, wherein the porous heating element is configured to include a porous conductor having continuous pores and can be energized through the porous conductor. element.   The gas sorption recovery element according to claim 2, wherein the porous heating element and the porous conductor are integrally formed from a common porous body.   The gas sorption recovery element according to any one of claims 1 to 3, comprising at least two or more porous heating elements, wherein the selected one or more heating elements can be energized to generate heat. .   The gas sorption recovery element according to any one of claims 1 to 4, wherein the gas sorbent layer is formed by coating the surface of pores with a zeolite powder through a binder.   The gas sorption recovery element according to any one of claims 2 to 5, further comprising an electrode portion connected to the porous conductor with a required area. The common porous body is
A skeleton having an outer shell provided with heat generation or conductivity in a predetermined region and a core made of a hollow or / and conductive material,
The gas sorption recovery element according to any one of claims 3 to 6, wherein the skeleton constitutes a three-dimensional network structure in which the skeleton is continuously integrated.   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 claim 7, which is constant.   The skeleton is formed by providing a plating layer or a metal coating layer on the surface of a three-dimensional knitted resin and erasing the resin. Gas sorption recovery element.   The gas storage according to any one of claims 7 to 9, wherein the exothermic outer shell is formed of an alloy containing Ni of 50 to 95% and Cr of 5 to 50%. Arrival collection element.   The exothermic outer shell is obtained by alloying by diffusing Cr into a predetermined part of a metal porous body that is mainly composed of Ni and can constitute a conductor, and imparts heat generation. The gas sorption recovery element according to any one of claims 7 to 10.   The exothermic outer shell is formed by laminating a second outer shell made of Cr on a predetermined portion of the first outer shell made of Ni, and then performing a predetermined heat treatment to form the first outer shell. The gas storage according to any one of claims 7 to 11, wherein the outer shell of the first shell and the second outer shell are diffused and alloyed to impart heat generation. Arrival collection element. A method for producing a gas sorption recovery element comprising a porous heating element and a porous conductor integrally, and at least a gas sorbent layer provided on the pore surface of the porous heating element,
An alloying step for forming the porous heating element by alloying a predetermined region of the porous body that can constitute the porous conductor;
And a gas sorbent layer forming step of providing a gas sorbent layer on the pore surface of the porous heating element. A method for producing a gas sorption recovery element comprising a porous heating element and a porous conductor integrally, and at least a gas sorbent layer provided on the pore surface of the porous heating element,
A conductor forming step of forming the porous conductor by providing a conductive layer on a surface of a predetermined region of the porous heating element that can constitute 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 claim 1.

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