JP5737587B2 - Power generator - Google Patents

Description

  The present invention relates to a power generation device using volume change based on gas adsorption / desorption.

  In recent years, from the viewpoint of environmental problems, resource saving and energy saving have attracted attention, and development of technologies for using various energy resources to replace fossil fuels is progressing. Among them, a method that uses sunlight, which is a typical natural energy, has attracted attention. For example, a method of converting solar energy into heat energy and taking it out as mechanical energy, or a method of converting it into electrical energy has been proposed.

  However, when sunlight is used as energy, the energy conversion efficiency is important, so although there are many systems proposed, the basic methods are limited from a practical standpoint. Currently. In other words, when using sunlight as thermal energy, the heat source is generally not very high, apart from a large-scale solar heat plant equipped with a large-scale concentrating device, and is considerably lower than the boiling point of water. It has become. Therefore, an engine that can efficiently extract mechanical energy from such a low-temperature heat source is required.

  As an engine that uses sunlight and is driven by a low-temperature heat source, for example, Patent Document 1 proposes a method using sunlight as an energy source that causes a phase change from liquid to gas. A method is described in which gas is generated by irradiation and the rotor is rotated using buoyancy generated by vaporization. In Patent Document 2, low temperature thermal energy such as solar heat is collected by a heat pump and supplied to an external combustion engine driven by thermal energy provided on the high temperature side and the low temperature side to drive the external combustion engine. A method for obtaining power is illustrated.

  As a method for generating power by efficiently driving with a low-temperature heat source, for example, in Patent Document 3, in a Stirling engine method with extremely high thermal efficiency, the basic principle for inducing the induction of gas pressure fluctuation is not an inorganic porous material but gas thermal expansion. Have proposed that the amount of gas adsorbed to the adsorbent varies according to the temperature change of the adsorbent, and that the temperature on the high temperature side can be made lower than the conventional one.

JP 2007-46484 A JP 2003-184650 A JP 7-217497 A

  However, in the above-mentioned Patent Document 1, a method is proposed in which a liquid is heated by sunlight to generate steam and the buoyancy of the steam in the liquid is used. However, the sunlight needs to pass through the liquid. In addition, heat is used to increase the temperature of liquids other than the liquid that evaporates when the liquid is used as a vapor, and the rotational resistance is large because of the rotation in the liquid. An engine with high exchange efficiency is difficult.

  Patent Document 2 proposes a method in which a compressed gas produced by a compressor is heated and expanded by concentrated light to rotate a turbine. However, complicated and large facilities such as a compressor and a turbine are required, and a high-pressure gas is used as a working medium. Therefore, there is a problem that a large apparatus is unavoidable because strength and hermeticity enough to withstand high pressure are required.

  In Patent Document 3, the cylinder is heated from the outside and the adsorbent is heated by this heat. However, since heat is transmitted through the air layer, heat transfer efficiency is low and energy loss is large. For this reason, although it is lower than before, a high heating temperature of 200 ° C. is required, and it is difficult to obtain such a high temperature from sunlight. There is also a problem in terms of durability since the adsorbent part that is easily crushed is movable in terms of apparatus.

  The present invention has been made in view of the problems of the prior art, and an object thereof is to propose a power generation device that can efficiently convert electromagnetic waves such as sunlight into kinetic energy with a simple device.

That is, the power generation device of the present invention is a process in which an adsorbed gas capable of adsorbing / desorbing gas is irradiated with electromagnetic waves, whereby the adsorbed gas is desorbed from the adsorbent and the volume of the gas expands. The volume change due to the repetition of the process in which the gas is adsorbed by the adsorbent and the volume of the gas contracts is taken out as a power source by blocking the electromagnetic wave.

And the power generator by the 1st means of this invention is characterized by the said adsorbent containing a bridge | crosslinking polyacrylate type | system | group polymer compound.

Moreover, the power generator according to the second means of the present invention is characterized in that the adsorbent includes a photothermal conversion material.

The power generation device according to the third means of the present invention includes an adsorbent (1) capable of adsorbing / desorbing gas, and an electromagnetic wave transmission window (8) capable of transmitting electromagnetic waves. An adsorbent holding part (2), a cylinder (3) connected to the adsorbent holding part (2), a piston (4) fitted in the cylinder and reciprocally movable, and an electromagnetic wave shielding plate capable of switching between electromagnetic wave irradiation and interruption (6), and a gas adsorbed / desorbed by the adsorbent (1) is enclosed in the cylinder (3), and the adsorbent (1) is irradiated with electromagnetic waves, The adsorbed gas is desorbed from the adsorbent, the volume expands and the piston (4) is pushed, and the electromagnetic wave is blocked by the electromagnetic wave shielding plate (6). The piston (4) is pulled The reciprocating motion of the piston (4) caused by repetition of processes and wherein the retrieving as a power source.

In the power generation apparatus according to the fourth means of the present invention, in any one of the first to third means, the electromagnetic wave is at least one selected from ultraviolet rays, visible rays, infrared rays, sunlight, heat rays, and radiant heat. It is characterized by that.

Moreover, the power generator according to the fifth means of the present invention is characterized in that the gas is water vapor in any one of the first to fourth means.

The power generator according to the sixth means of the present invention has means for cooling the adsorbent in any of the first to fifth means, and cools the adsorbent in the process of blocking electromagnetic waves. This is characterized in that adsorption is promoted.

In addition, the power generation apparatus according to the seventh means of the present invention is characterized in that in any one of the first to sixth means, switching between irradiation and blocking of electromagnetic waves is performed by the power generated by itself. To do.

The power generation system according to the eighth means of the present invention is characterized in that power is generated by the power generated by any one of the first to seventh means.

  An air conditioning system according to the ninth means of the present invention is characterized in that air conditioning is performed by power generated by any one of the first to seventh means.

  As described above, the present invention is a simple apparatus by efficiently desorbing / adsorbing gas to / from an adsorbent at low temperatures by using electromagnetic wave irradiation / blocking and utilizing the volume change of gas expansion / contraction associated therewith. Thus, the energy of electromagnetic waves can be efficiently converted into kinetic energy.

It is the schematic which shows an example of the motive power generator of this invention. It is the schematic which shows an example of the power generator of this invention which provided the means to cool an adsorbent. It is the schematic which shows an example of the motive power generator of this invention made to switch electromagnetic wave irradiation and interruption | blocking with the motive power which self generate | occur | produced. It is the schematic which shows an example of the system which produces electric power with the motive power which the power generation device of the present invention generated. It is the schematic which shows an example of the system which air-conditions with the motive power which the power generation device of this invention generate | occur | produced.

  The power generation device of the present invention makes it possible to use, as power, the change in the volume of the gas accompanying the adsorption / desorption of the gas by the adsorbent. That is, a process in which the gas adsorbed on the adsorbent capable of adsorbing / desorbing the gas is desorbed from the adsorbent and the volume of the gas expands, and the gas is adsorbed on the adsorbent and the gas Volume change due to repetition of the process of contracting the volume is taken out as a power source. In the power generation device of the present invention, in the process of desorbing the gas from the adsorbent, the gas is desorbed by supplying energy by irradiating the adsorbent with electromagnetic waves, and then the gas is adsorbed by the adsorbent. Then, the electromagnetic wave is cut off and gas is adsorbed.

  Hereinafter, embodiments of a power generation device, a power generation system, and an air conditioning system of the present invention will be described in detail with reference to the drawings. In the following description, components having the same functions, shapes, and the like, and constituent elements such as components are denoted by the same reference numerals and will not be described later. In addition, in order to simplify the drawings and the description, even components that are to be represented in the drawings may be omitted as appropriate without being specifically described in the drawings.

  First, the basic principle of the power generator of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing an example of the power generating device of the present invention, and the present invention is not limited to the configuration shown in the figure. 1 to 3 are illustrated with a crankshaft connected to the power generator of the present invention in order to facilitate understanding of the present invention.

  In the power generating device of the present invention shown in FIG. 1, the adsorbent holding part (2) having an electromagnetic wave transmission window (8) that holds the adsorbent (1) inside and can transmit the electromagnetic wave (5). ) And a cylinder (3) connected to the cylinder and a piston (4) reciprocatingly moving inside the cylinder, a sealed space is formed, in which gas adsorbed and desorbed by the adsorbent (1) is formed. It is enclosed.

  When the adsorbent (1) is irradiated with the electromagnetic wave (5) through the electromagnetic wave transmission window (8), the adsorbed gas is desorbed from the adsorbent (1) and the volume of the gas (7) is expanded. Next, when the electromagnetic wave (5) is blocked by the electromagnetic wave shielding plate (6), the gas (7) is adsorbed by the adsorbent (1) and the volume of the gas (7) contracts. The piston (4) reciprocates along with the volume change due to repeated expansion and contraction to generate power. This generated power can be converted into rotational motion by, for example, connecting the piston (4) to the crankshaft (9).

  Here, the electromagnetic wave (5) is not particularly limited, and any electromagnetic wave such as sunlight, ultraviolet rays, visible rays, infrared rays, white rays, heat rays, radiant heat, and microwaves can be used. Among them, sunlight, ultraviolet rays, visible rays, infrared rays, heat rays, and radiant heat can be efficiently used, and sunlight that is natural energy and does not affect the environment is most preferable.

  The gas (7) is not particularly limited as long as it is a gas that can be adsorbed on the adsorbent and desorbed from the adsorbent by the energy of electromagnetic waves, and can be appropriately selected in combination with the adsorbent. For example, water, ammonia, methyl alcohol, ethyl alcohol and the like can be mentioned. Among them, water, that is, water vapor, is most preferable because it has no problem even if it is released into the air as it is and does not affect the environment.

  Next, examples of the adsorbent (1) include an adsorbent substance and a substance containing a complex of the adsorbent substance and another substance. Examples of the adsorptive substance include inorganic porous materials such as silica gel, zeolite and activated alumina, inorganic salts such as lithium chloride and calcium chloride, or polyacrylic acid and its salt, polymethacrylic acid and its salt, polysulfonic acid and its Examples thereof include organic polymer compounds having a hydrophilic functional group such as a salt, polyphosphoric acid and a salt thereof, polyglutamic acid and a salt thereof, and polyacrylamide. These may be used alone or in combination of two or more. Examples of the composite of the adsorbing substance and other substances include particles, fibers, resin films, rubbers, and the like containing these adsorbing substances. Hereinafter, both the adsorptive substance and the complex of the adsorbent substance and another substance are collectively referred to as an adsorbent material.

  Moreover, as a form of an adsorbent, if it contains a fibrous adsorbent material, what processed these adsorbent materials into paper, a nonwoven fabric, a knitted fabric, etc. are mentioned. In addition, in the case of containing an adsorbent material such as a particulate form, those in which these adsorbent materials are carried on a carrier can be used. Here, examples of the carrier include paper, nonwoven fabric, knitted fabric, film, metal plate, porous material, or a honeycomb structure obtained by three-dimensionally molding a sheet-like material such as paper or film.

  In particular, when a honeycomb structure carrying an adsorbent material is used, the area for receiving electromagnetic waves can be widened, which is desirable as an adsorbent used in the present invention. Examples of the honeycomb structure include a hexagonal type, an OX type, a flex type, a bisecting type, and a feather type (hereinafter referred to as a corrugated type). Among them, a corrugated type that is easy to process, has a high processing speed, and is advantageous in terms of cost is preferable. Further, characteristics such as the size and length of the corrugated cell can be appropriately selected in consideration of the gas diffusion rate and the like.

  Among the adsorbent materials mentioned above, the gas adsorption amount is large, the adsorption speed is fast, the gas can be efficiently desorbed even with a small energy, and the performance is not easily lowered even after repeated adsorption and desorption. From the viewpoint of dynamic power generation. In the case of employing water vapor as the gas, among the adsorbing materials, those having hygroscopicity can be employed.In particular, from the above viewpoint, the organic polymer main chain having a hydrophilic polar group in the molecule is formed by a crosslinked structure. A three-dimensional structured organic polymer compound is preferred. Such an organic polymer compound sorbs a large amount of water vapor based on a sorption phenomenon. In the present invention, such a material is referred to as an organic polymer sorbent.

  Here, the sorption phenomenon is a phenomenon in which the gas concentration in the solid phase is higher than that in the gas phase at the interface between the gas and the solid in a system where the gas and the solid are in contact with each other. The phenomenon of entering the solid through the solid surface layer is called absorption, but this adsorption and absorption occur simultaneously. That is, when water vapor, which is a gaseous water molecule, acts on the organic polymer sorbent, the water molecule is adsorbed by the highly hydrophilic polar group of the sorbent, and further enters the sorbent and is absorbed. go.

  In such organic polymer-based sorbents, the three-dimensional structure due to the crosslinked structure has moderate flexibility, so that when water is absorbed, it swells as water molecules are absorbed and a large amount of water molecules are absorbed into the sorbent. It can be taken up, and when moisture is released, it can shrink and return to its original structure as water molecules are released. That is, the organic polymer sorbent has both a high moisture absorption rate and excellent durability against repeated moisture absorption and release, and is an adsorbent material suitable for the power generation device of the present invention.

  Among such organic polymer sorbents, the polyacrylic acid salt having a cross-linked structure can easily achieve desirable characteristics such as high saturation moisture absorption and low temperature, that is, moisture can be released even at low energy. As the adsorptive material used for the above, it can be particularly preferably employed. In the present invention, the polyacrylic acid salt having such a crosslinked structure is also referred to as a crosslinked polyacrylate polymer compound.

  In the crosslinked polyacrylate polymer compound, a carboxyl group which is a hydrophilic polar group and a cation constitute a salt. The cation constituting the salt is not particularly limited, and examples thereof include alkali metals such as Li, Na, K, Rb, and Cs, alkaline earth metals such as Be, Mg, Ca, Sr, and Ba, Cu, Zn, and Al. Other metals such as Mn, Ag, Fe, Co, and Ni, organic cations such as NH4 and amine, and the like, and two or more of these cations may be used simultaneously. Among these, if K is selected as the cation, the moisture absorption / release rate increases, which is advantageous in terms of power generation.

  In the crosslinked polyacrylate polymer compound, a carboxyl group constituting a salt with a cation, that is, a salt-type carboxyl group is a highly hydrophilic polar group suitable for developing hygroscopicity, and is high When trying to obtain moisture absorption / release performance, it is preferable to contain as many salt-type carboxyl groups as possible. However, in order to achieve high durability and moisture absorption rate simultaneously with the moisture absorption amount, it is necessary to appropriately balance the ratio with the crosslinked structure.

  That is, when the amount of the salt-type carboxyl group of the crosslinked polyacrylate polymer compound exceeds 10.0 mmol / g, the ratio of the crosslinked structure that can be introduced is too small, which is close to a so-called superabsorbent resin. In some cases, the moisture absorption performance is lowered, the form stability is inferior, and sufficient durability cannot be obtained. The amount of the salt-type carboxyl group that gives more preferable results from the above viewpoint is 9.5 mmol / g or less.

  On the other hand, when the amount of the salt-type carboxyl group is small, the hygroscopic performance decreases, and in particular, when it is lower than 1.0 mmol / g, the sufficient hygroscopic performance may not be obtained. When the amount of the salt-type carboxyl group is 3.0 mmol / g or more, the superiority of the hygroscopic performance is remarkable as compared with other existing hygroscopic materials, and a more preferable result is given.

  The method for introducing a salt-type carboxyl group in such a crosslinked polyacrylate polymer compound is not particularly limited. For example, another monomer capable of homopolymerizing or copolymerizing a monomer having a salt-type carboxyl group. A method of obtaining a polymer by copolymerization with a polymer (first method), a method of obtaining a polymer having a carboxyl group and then changing it to a salt form (second method), a functional group that can be derived to a carboxyl group A method of polymerizing a monomer having a group and converting the functional group of the obtained polymer into a carboxyl group by chemical modification and further changing to a salt type (third method), or the above three methods by graft polymerization And the like.

  As a method for polymerizing a monomer having a salt-type carboxyl group in the first method, for example, correspondence of a monomer containing a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinylpropionic acid, etc. Polymerizing a single salt-type monomer, or two or more of these monomers, or a mixture of the same type but a carboxylic acid type and a corresponding salt type, and further these monomers And a method of copolymerizing with another monomer copolymerizable with the monomer.

  In addition, the method of converting to a salt form after obtaining a polymer having a carboxyl group in the second method is, for example, a homopolymer of an acid type monomer containing a carboxyl group as described above, or This is a method in which a copolymer comprising two or more monomers or a copolymer with another copolymerizable monomer is obtained by polymerization and then converted into a salt form. There is no particular limitation on the method for converting the carboxyl group into a salt form, and the obtained acid type polymer has an alkali metal ion such as Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, etc. Ion exchange is performed by the action of alkaline earth metal ions, other metal ions such as Cu, Zn, Al, Mn, Ag, Fe, Co and Ni, and organic cations such as NH4 and amine compounds. It can be converted by such a method.

  Examples of the method of introducing a carboxyl group by the third chemical modification method include, for example, a homopolymer of a monomer having a functional group that can be modified to a carboxyl group by a chemical modification treatment, or a copolymer comprising two or more types, Alternatively, there is a method in which a copolymer with another copolymerizable monomer is polymerized, and the resulting polymer is modified to a carboxyl group by hydrolysis. The above-described method for forming a salt form is applied to the carboxyl group formed. Monomers that can take such a method include monomers having nitrile groups such as acrylonitrile and methacrylonitrile; carboxylic acid groups such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and vinyl propionic acid. Examples thereof include anhydrides, ester derivatives, amide derivatives, and ester derivatives having crosslinkability.

  Examples of the anhydride of a monomer having a carboxylic acid group include maleic anhydride, acrylic anhydride, methacrylic anhydride, itaconic anhydride, phthalic anhydride, N-phenylmaleimide, N-cyclomaleimide and the like.

  Examples of ester derivatives of monomers having a carboxylic acid group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, lauryl, pentadecyl, cetyl, stearyl, behenyl, 2-ethylhexyl, isodecyl, isoamyl and the like. Ester derivatives; methoxyethylene glycol, ethoxyethylene glycol, methoxy polyethylene glycol, ethoxy polyethylene glycol, polyethylene glycol, methoxypropylene glycol, propylene glycol, methoxy polypropylene glycol, polypropylene glycol, methoxy polytetraethylene glycol, polytetraethylene glycol, polyethylene glycol Polypropylene glycol, polyethylene glycol-polytetraethylene Alkyl ether ester derivatives such as recall, polyethylene glycol-polypropylene glycol, polypropylene glycol-polytetraethylene glycol, butoxyethyl; cyclohexyl, tetrahydrofurfuryl, benzyl, phenoxyethyl, phenoxypolyethylene glycol, isobornyl, neopentyl glycol benzoate, etc. Cyclic compound ester derivatives; hydroxyalkyl ester derivatives such as hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyphenoxypropyl, hydroxypropylphthaloylethyl, chloro-hydroxypropyl; aminoalkyl esters such as dimethylaminoethyl, diethylaminoethyl, and trimethylaminoethyl Derivative; (Meth) acryloyloxyethyl Koh Acid, carboxylic acid alkyl ester derivatives such as (meth) acryloyloxyethyl hexahydrophthalic acid; phosphoric acid groups or phosphate esters such as (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxyethyl acid phosphate Alkyl ester derivatives containing groups;

  Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin dimethacrylate, 2-hydroxy-3-acryl Leuoxypropyl (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, neopentyl glycol di ( Crosslinkable alkyl esters such as (meth) acrylate, 1,10-decanediol di (meth) acryl, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate; trifluoroethyl, Fluorinated alkyl ester derivatives such as tetrafluoropropyl, hexafluorobutyl and perfluorooctylethyl can be mentioned.

  Examples of the amide derivative of a monomer having a carboxylic acid group include amide compounds such as (meth) acrylamide, dimethyl (meth) acrylamide, monoethyl (meth) acrylamide, and normal t-butyl (meth) acrylamide. Other methods for introducing a carboxyl group by chemical modification include oxidation of alkenes, alkyl halides, alcohols, aldehydes, and the like.

  The method for introducing a salt-type carboxyl group by the hydrolysis reaction of the polymer in the third method is not particularly limited, and known hydrolysis conditions can be used. For example, a salt-type carboxyl group is introduced into a crosslinked polymer obtained by polymerizing the above monomers using a basic aqueous solution of an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, potassium hydroxide or ammonia. Method or reaction with mineral acids such as nitric acid, sulfuric acid, hydrochloric acid or organic acids such as formic acid, acetic acid, etc. to form carboxylic acid groups, and then mixed with alkali metal salts to introduce salt-type carboxyl groups by ion exchange The method of doing is mentioned. Of these, a hydrolysis method using potassium hydroxide is preferred, in which a potassium salt-type carboxyl group having an excellent moisture absorption rate can be easily obtained. In addition, about the conditions used as 1.0-10.0 mmol / g, it determines by clarifying the relationship between reaction factors, such as reaction temperature, density | concentration, time, and the amount of salt-type carboxyl groups introduce | transduced by experiment. be able to.

  In addition, the crosslinked structure of the organic polymer sorbent may be any structure such as crosslinking by covalent bond, ionic crosslinking, interaction between polymer molecules or crosslinking by crystal structure. As for the method of introducing the crosslinking, the crosslinking introduction method by copolymerizing the crosslinkable monomer in the polymerization step of the monomer to be used, or the monomer is first polymerized, and then the chemical reaction or physical And a post-crosslinking method such as introduction of a cross-linked structure by specific energy. Among them, in the method using a crosslinkable monomer in the polymerization stage of the monomer, or the method by chemical post-crosslinking after obtaining the polymer, it is possible to introduce strong cross-linking by a covalent bond, It is preferable in that it is difficult to undergo physical and chemical modification accompanying moisture absorption and release.

  In the method of using a crosslinkable monomer in the monomer polymerization stage, particularly in the case of the above-described crosslinked polyacrylate polymer compound, the monomer having a carboxyl group described above or capable of being modified to a carboxyl group A cross-linked polymer having a cross-linked structure based on a covalent bond can be obtained by performing copolymerization using a cross-linkable monomer that can be copolymerized. However, in this case, the acidic conditions indicated by the acrylic acid monomer or the like, or crosslinks that are not or are not susceptible to chemical influences (eg hydrolysis) upon modification to the carboxyl group in the polymer. It must be a sex monomer.

  There are no particular limitations on the crosslinkable monomer that can be used in the method of using a crosslinkable monomer in the polymerization step of the monomer. For example, glycidyl methacrylate, N-methylolacrylamide, triallyl isocyanurate, triallyl cyanurate, divinyl Listed are crosslinkable vinyl compounds such as benzene, hydroxyethyl methacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and methylenebisacrylamide. Cross-linked structures with isocyanurate, triallyl cyanurate, divinylbenzene, and methylene bisacrylamide are also used for hydrolysis to introduce carboxyl groups to cross-linked polymers containing them. Histological to is of a desirable and stable.

  Further, the method by post-crosslinking is not particularly limited. For example, a nitrile group contained in a nitrile polymer having a nitrile group-containing vinyl monomer content of 50% by weight or more is reacted with a hydrazine compound or formaldehyde. A post-crosslinking method can be mentioned. In particular, the cross-linked structure introduced by the hydrazine compound is stable to acids and alkalis, and the formed cross-linked structure itself is hydrophilic so that it can contribute to the improvement of hygroscopicity. It is extremely excellent in that it can introduce a strong crosslink that can maintain a porous form. In addition, although the detail is not identified regarding the crosslinked structure obtained by this reaction, it is estimated that it is based on a triazole ring structure or a tetrazole ring structure.

  The vinyl monomer having a nitrile group here is not particularly limited as long as it has a nitrile group, and specifically, acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, cyanide. And vinylidene chloride. Among them, acrylonitrile is most preferable because it is advantageous in terms of cost and has a large amount of nitrile groups per unit weight.

  The method for introducing the crosslinking by reaction with the hydrazine compound is not particularly limited as long as the desired crosslinked structure is obtained. The concentration of the nitrile polymer and the hydrazine compound during the reaction, the solvent to be used, the reaction Time, reaction temperature, etc. can be suitably selected as necessary. Of these, when the reaction temperature is too low, the reaction rate becomes slow and the reaction time becomes too long, and when the reaction temperature is too high, plasticization of the nitrile polymer occurs, which is imparted to the polymer. There may be a problem that the former form is destroyed. Therefore, a preferable reaction temperature is 50 to 150 ° C, more preferably 80 to 120 ° C. Moreover, there is no limitation in particular also about the part of the nitrile polymer made to react with a hydrazine type compound, and it can select suitably according to the use and the form of this polymer. Specifically, the reaction can be appropriately selected such as reacting only on the surface of the polymer, reacting to the entire core, or reacting with a specific portion limited. The hydrazine compounds used herein include hydrazine salts such as hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine nitrate, hydrazine hydrobromide, hydrazine carbonate, and ethylenediamine, guanidine sulfate, guanidine hydrochloride, guanidine nitrate. And hydrazine derivatives such as guanidine phosphate and melamine.

  Further, as described above, in the present invention, it is desirable that gas can be efficiently desorbed from the adsorptive material by electromagnetic wave energy. For this purpose, it is preferable that a photothermal conversion material is contained in the adsorbent. In such a case, the electromagnetic wave energy is once converted into thermal energy by the photothermal conversion material, and the gas adsorbed on the adsorptive material is desorbed by this thermal energy, and the volume of the gas expands. On the other hand, by blocking electromagnetic waves, the gas is adsorbed by the adsorptive material and the volume of the gas contracts. At this time, the conversion from electromagnetic energy to thermal energy in the photothermal conversion material is very fast, and the photothermal conversion material and the vicinity thereof rapidly increase in temperature. On the other hand, if the electromagnetic wave is cut off, the photothermal conversion function is lost and the temperature decreases rapidly. Therefore, it is possible to efficiently convert energy.

  The photothermal conversion material is not particularly limited as long as it is a material that can absorb electromagnetic waves and convert it into heat, and examples thereof include photothermal conversion materials such as inorganic substances, pigments, dyes, and infrared absorbers. Examples of inorganic substances include carbides, oxides, sulfides, and carbon allotropes. Examples of the carbide include titanium carbide, zirconium carbide, hafnium carbide, silicon carbide, boron carbide, and tantalum carbide. Examples of the oxide include titanium oxide, silicon oxide, chromium oxide, zirconium oxide, iron oxide, copper oxide, and oxide. Silver, chromium oxide, lead oxide, etc. are mentioned. Examples of sulfides include titanium sulfide, silicon sulfide, chromium sulfide, zirconium sulfide, iron sulfide, copper sulfide, silver sulfide, chromium sulfide, and lead sulfide. Carbon allotropes include graphite, carbon graphite, and carbon nanotube. , Furnace black, acetylene black and the like. In addition to these, mica, calcite, blackened silver, iron powder and the like can be cited as inorganic substances.

  Examples of the pigment include natural pigments, fluorescent pigments, organic pigments such as inorganic pigments, azo pigments, and polycyclic pigments. Among these, examples of the inorganic pigment include carbon black and titanium black. Examples of azo pigments include insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, and polycyclic pigments include phthalocyanine pigments, perylene and perinone pigments, thioindigo pigments, and quinacridone pigments. Examples thereof include pigments, dioxazine pigments, isoindolinone pigments, and quinophthalone pigments. In addition to these, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments and the like are also included as pigments.

  Examples of the dye include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, naphthalocyanine dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, indolenine dyes, cyanine dyes, naphthoquinone dyes, and the like. Can do. Infrared absorbers include pyrylium compounds, arylbenzo (thio) pyrylium salt compounds, trimethine thiapyrylium salts, pentamethine thiopyrylium salts, cyanine dyes, squarylium dyes, croconium dyes, polymethine dyes, azurenium dyes Naphthoquinone dyes, anthraquinone pigments, dithiol nickel complexes, metal thiolate complexes, nickel thiolates, and the like.

  Furthermore, synthetic fibers and natural fibers containing the above-described light-to-heat conversion substance, resin film, rubber, or the like can also be used as the light-to-heat conversion material employed in the present invention.

  Among the photothermal conversion materials described above, the average value of the spectral reflectance for light in the visible to near infrared region (wavelength 380 to 2500 nm) is preferably 50% or less, more preferably 30% or less. In particular, a carbon allotrope or an inorganic compound which is a black material having a high absorption rate over all wavelengths of sunlight and excellent in light resistance is preferably used. Specifically, blackened silver, graphite, carbon black, carbon graphite, carbon nanotube, furnace black, acetylene black, iron oxide, and the like are preferable photothermal conversion materials. Examples of the form of the photothermal conversion material used in the present invention include fine particles, fibers, and films.

  Moreover, the size of the photothermal conversion material is preferably smaller because the contact interface increases and thermal energy conduction is improved. However, if the size is too small, it is difficult to absorb electromagnetic waves and the heat generation amount is reduced. In the case of a particulate photothermal conversion material, the particle diameter is preferably 0.01 μm to 20 μm, more preferably 0.05 to 5 μm.

  As described above, the electromagnetic energy is converted into thermal energy by the photothermal conversion material, and this thermal energy is used as energy for desorbing gas from the adsorptive material. Therefore, it is desirable from the aspect of increasing the desorption efficiency that heat energy generated from the photothermal conversion material can be efficiently conducted to the adsorptive material.

  For this purpose, in the adsorbent, the distance between the adsorbent material and the photothermal conversion material is small, and there is no intervening material with low thermal conductivity such as an air layer, that is, at least a part of these materials. It is preferably in a state of being in direct contact or in a state of being in close proximity via a binder. Here, although it is not easy to directly measure the distance between the adsorptive material and the photothermal conversion material, the ratio of the weight of the binder to the total weight of the adsorbent material and the photothermal conversion material can be used as an index. That is, the smaller the ratio, the smaller the binder amount, and the shorter the distance between the adsorptive material and the photothermal conversion material. As the state of being in close proximity through the binder, when the total weight of the adsorbent material and the photothermal conversion material is 100 parts by weight, the binder is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, and still more preferably The state is 30 parts by weight or less, most preferably 10 parts by weight or less.

  Specific examples of the state of direct contact include a state in which the photothermal conversion material is dispersed using the adsorbent material itself as a continuous phase, and a photothermal conversion material is dispersed or coated on the continuous phase of the adsorbent material itself. Examples thereof include a state where the adsorbent material is dispersed with the photothermal conversion material itself as a continuous phase, and a state where the adsorbent material is dispersed or coated on the continuous phase of the photothermal conversion material itself.

  In addition, the adsorbent material and the photothermal conversion material are exchanged in a state where the adsorbent material is impregnated or coated on a substrate made of a fibrous photothermal conversion material, a film-like photothermal conversion material, or the like. An example of a state of direct contact is also possible.

  On the other hand, specific examples of the state of being close to each other through the binder include [1] a state in which the adsorbent material and the photothermal conversion material are dispersed with the binder as a continuous phase, and [2] an adsorption with the binder as a continuous phase. A state in which the layer in which the photosensitive material is dispersed and the layer in which the photothermal conversion material is dispersed with the binder as the continuous phase are laminated; [3] the adsorbent material is dispersed with the binder as the continuous phase; A state in which the photothermal conversion material is dispersed or coated on the phase, or a state in which the adsorptive material and the photothermal conversion material are replaced with each other in the states [2] and [3] can be exemplified.

  In the state [2] or [3] above, if the upper layer or coating is too thick, problems such as hindering the function of the lower layer or the material on the side to be coated or facilitating dropping off may occur. There is a case. Specifically, when the thickness of the upper layer or coating is 0.3 mm or less, good results are often obtained.

  The binder is not particularly limited, but for organic systems, acrylic resins such as polymethyl methacrylate, polycarbonate, polystyrene, vinyl chloride / vinyl acetate copolymers, vinyl resins such as polyvinyl alcohol, polyvinyl butyral, Polyester, polyvinyl chloride, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, aramid, polyurethane, epoxy resin, urea / melamine resin, etc., inorganic materials include colloidal silica, water glass, aluminum phosphate, etc. .

  Moreover, the state where the state of being in direct contact and the state of being in close proximity via a binder are mixed is also preferable. As a specific example, the adsorbent material and the binder are both continuous phases, and the photothermal conversion material is dispersed in these continuous phases. In this example, the continuous phase of the adsorbent material and the continuous phase of the binder are entangled in a three-dimensional spread, and the photothermal conversion material is dispersed in any continuous phase. . Examples of such a state include an example in which a crosslinked polyacrylic acid polymer compound in the form of an aqueous dispersion is used as the adsorbing material. In this case, when the total weight of the compound, the photothermal conversion material, the binder, and other additives is 100 parts by weight and the amount is 70 parts by weight or more, the adsorptive material tends to be a continuous phase.

  The content ratio of the adsorbent material and the photothermal conversion material is not particularly limited as long as the required function is expressed. However, from the viewpoint of preventing the amount of adsorption from becoming too small while effectively utilizing the thermal energy converted from the photothermal conversion material for desorption of gas from the adsorbent material, the preferred content of each material is adsorption When the total weight of the luminescent material and the photothermal conversion material is 100 parts by weight, the adsorptive material is 50 to 99.5 parts by weight, and one photothermal conversion material is 0.5 to 50 parts by weight. The material is 70 to 99.5 parts by weight, the one photothermal conversion material is 0.5 to 30 parts by weight, more preferably the adsorbent material is 90 to 99.5 parts by weight, and the other photothermal conversion material is 0.00. 5 to 10 parts by weight.

  In addition, the amount of binder in the case of using a binder is from the viewpoint of avoiding that the adsorbent material is covered with the binder and reducing the adsorption / desorption performance, and from the viewpoint of bringing the adsorbent material and the photothermal conversion material in close proximity. It is desirable to reduce the amount of the binder. When the total weight of the adsorbent material and the photothermal conversion material is 100 parts by weight as described above, the binder is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, and still more preferably Is preferably 30 parts by weight or less, and most preferably 10 parts by weight or less. However, if the amount of the binder is too small, the adsorptive material or the photothermal conversion material cannot be sufficiently fixed to the carrier or the like, and there may be a problem that these materials fall off. For this reason, the lower limit of the binder amount in the case of using a binder is preferably 1 part by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the total weight of the adsorptive material and the photothermal conversion material. It is desirable to do.

  In addition, the energy converted from electromagnetic waves such as sunlight into heat by the photothermal conversion material is not so large, and when a special operation such as condensing is not performed, it is obtained at a relatively low temperature of 40 ° C. to 70 ° C. Only. For this reason, when the photothermal conversion material is contained in the adsorbent of the present invention, the adsorbent material preferably has a property that can be easily desorbed even at such a low temperature. Examples of the adsorptive material include the organic polymer sorbents described above, and among them, a crosslinked polyacrylate polymer compound is preferable.

  Next, the adsorbent holding part (2) and the cylinder (3) are not particularly limited except that they have sufficient strength to withstand the volume expansion / contraction of gas and there is no gas leakage. As for the material, any of glass, resin and metal can be used. However, if the material other than the electromagnetic wave transmission window is made of a material that transmits electromagnetic waves, the electromagnetic wave shielding plate alone may not be able to sufficiently block the electromagnetic waves. Therefore, a colored resin or metal that can block electromagnetic waves may be used as the material. It is preferable to use it. Further, since the gas density is increased by desorption of the gas inside the adsorbent holding part and the cylinder, the gas tends to condense on the inner wall surface due to the temperature difference from the outside air temperature. For this reason, it is preferable to cover the periphery with a heat insulating material so as not to be affected by the outside air temperature.

  Examples of such heat insulating materials include cellulose fibers, lightweight soft wood fiber boards, carbonized foam cork, cellulose wool, coconut fibers, cotton-like wood fibers, flux fibers, hamph fibers, cotton, wool and other natural heat insulation materials, rigid urethane foams, Extruded polystyrene foam, beaded polystyrene, highly foamed polyethylene, foamed calcium carbide, phenol foam, plastic insulation such as foam glass, and mineral insulation such as glass wool and rock wool.

  Further, the adsorbent holding part (2) is provided with an electromagnetic wave transmission window (8) since it is necessary to allow electromagnetic waves to reach the adsorbent. The electromagnetic wave transmission window is not particularly limited as long as it can transmit electromagnetic waves and can withstand expansion / contraction, and transparent glass, resin, and the like can be appropriately selected. In particular, glass is preferable in terms of light resistance and durability. In addition, since there is a possibility that gas condensation occurs due to the influence of the outside temperature as described above, it is particularly preferable to have a heat insulating property that can reduce the influence of the outside temperature, for example, a pair glass, a vacuum double glass, etc. Can be mentioned.

  Next, the electromagnetic wave shielding plate (6) is not particularly limited as long as the material, shape, and the like can block electromagnetic waves. For example, a metal plate, a colored resin plate, or the like can be used. In addition, the electromagnetic wave shielding plate needs to be able to alternately switch between irradiation and shielding of electromagnetic waves, but there is no particular limitation on the switching method, and the electromagnetic wave shielding plate can be rotated or laterally swung. In addition to such a mechanical method, a method of incorporating liquid crystal into an electromagnetic wave shielding plate and electrically switching between coloring and transparency can be employed.

  As described above, the power generation device of the present invention takes out gas volume expansion and contraction as a power source. There is no particular limitation on the method of taking out the volume expansion and contraction as a power source. For example, a method of taking out as a rotational motion by substituting the change in volume with the motion of the piston by the cylinder and the piston and interlocking this with the crankshaft. .

  FIG. 2 is a schematic view of an example of an embodiment of the present invention in which the adsorbent holding part (2) can be cooled from the outside. The electromagnetic wave shielding plate (6) blocks the electromagnetic wave (5) to the electromagnetic wave transmission window (8), and at the same time, the fan (10) rotates and the cooling air (11) is generated to cool the adsorbent holding part (2). To do. By this cooling, the adsorbent (1) in the process in which gas is adsorbed by blocking electromagnetic waves is cooled, and the efficiency of adsorption is further improved. As a result, the contraction force is increased and the kinetic energy is increased.

  FIG. 3 is a schematic diagram of an example of an embodiment in which switching between electromagnetic wave irradiation and blocking can be performed by power generated by itself. One of the cross-shaft gears (13) is fixed to the crankshaft (9) that converts the reciprocating motion of the piston (4) into rotary motion, and the other cross-shaft gear (13) crosses the crankshaft (9). The rotating shaft (12) is fixed. An electromagnetic wave shielding plate (6) is fixed to the rotating shaft (12), and rotates simultaneously with the rotation of the rotating shaft (12). The period of the rotation of the crankshaft (9), the rotation of the rotation shaft (12), and the rotation of the electromagnetic wave shielding plate (6) can be adjusted as appropriate. In this embodiment, it is possible to operate with only electromagnetic wave energy without using external power or the like. When sunlight is used as electromagnetic waves, a natural energy utilization system that does not give any load to the environment is obtained.

  FIG. 4 is a schematic diagram illustrating an example of a system that generates power using the power generated by the power generation device of the present invention. This is a system in which a generator (14) is connected to a crankshaft (9) that converts motive power generated by the power generation device of the present invention into rotational energy, and rotational energy is extracted as electric energy. When sunlight is used as electromagnetic waves, it becomes an environment-friendly power generation system using natural energy.

  FIG. 5 is a schematic diagram showing an example of a system that performs air conditioning with the power generated by the power generation device of the present invention. An air conditioning fan (16) is attached to a crankshaft (9) that converts power generated by the power generation device of the present invention into rotational energy, and is used as power for exchanging outside air. Although not shown, air conditioning for cooling and heating can be performed by connecting the rotating shaft of the heat pump to the crankshaft (9) instead of the air conditioning fan (16). When sunlight is used as electromagnetic waves, it becomes an environment-friendly air conditioning system using natural energy.

DESCRIPTION OF SYMBOLS 1 Adsorbent 2 Adsorbent holding part 3 Cylinder 4 Piston 5 Electromagnetic wave 6 Light shielding plate 7 Gas 8 Electromagnetic wave transmission window 9 Crankshaft 10 Fan 11 Cooling air 12 Rotating shaft 13 Crossed shaft gear 14 Generator 15 Housing 16 Air conditioning fan 17 Ventilation Flow

Claims (9)

By irradiating the adsorbent capable of adsorbing / desorbing the gas with electromagnetic waves, the process of expanding the volume of the gas by desorbing the adsorbed gas from the adsorbent, and blocking the electromagnetic waves, A power generation device for taking out as a power source a volume change due to repetition of a process in which the gas is adsorbed by the adsorbent and the volume of the gas contracts , wherein the adsorbent comprises a crosslinked polyacrylate polymer compound A power generator characterized by including . By irradiating the adsorbent capable of adsorbing / desorbing the gas with electromagnetic waves, the process of expanding the volume of the gas by desorbing the adsorbed gas from the adsorbent, and blocking the electromagnetic waves, A power generation device for taking out as a power source a volume change due to repetition of a process in which the gas is adsorbed by the adsorbent and the volume of the gas contracts, wherein the adsorbent includes a photothermal conversion material. Power generator. An adsorbent holding part (2) including an adsorbent (1) capable of adsorbing / desorbing gas and having an electromagnetic wave transmission window (8) capable of transmitting electromagnetic waves, and a cylinder ( 3), a piston (4) that is fitted in the cylinder and can reciprocate, and an electromagnetic wave shielding plate (6) that can switch between irradiation and shielding of electromagnetic waves, and is adsorbed in the cylinder (3) The gas adsorbed / desorbed by the material (1) is enclosed, and when the adsorbent (1) is irradiated with electromagnetic waves, the adsorbed gas is desorbed from the adsorbent and the volume expands. The piston (4) is pushed by the process of pushing the piston (4) and the electromagnetic wave is blocked by the electromagnetic wave shielding plate (6). 4) Power generation apparatus characterized by taking out as a power source backward movement. The power generation device according to any one of claims 1 to 3, wherein the electromagnetic wave is at least one selected from ultraviolet rays, visible rays, infrared rays, sunlight, heat rays, and radiant heat. The power generator according to any one of claims 1 to 4 , wherein the gas is water vapor. It has a means for cooling the adsorbent in the process of blocking electromagnetic waves, the power generating device according to any one of claims 1-5, characterized in that to promote the adsorption by cooling the adsorbent. Due to its own generated power, the power generating device according to claim 1, characterized in that for switching and blocking the irradiation of electromagnetic waves 6. Power generation system characterized by the power generation by the power generated by the power generating device according to any one of claims 1 to 7. An air conditioning system that performs air conditioning with the power generated by the power generation device according to any one of claims 1 to 7 .

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