Patent Application
20190201832
The present invention relates to an adsorbent, a method for producing the same, a method for removing carbon dioxide, a device for removing carbon dioxide, and an air conditioner.
In recent years, global warming caused by emission of greenhouse effect gases has become a global problem. Examples of greenhouse effect gases may include carbon dioxide (CO2), methane (CH4), and fluorocarbons (CFCs and the like). Among the greenhouse effect gases, the effect of carbon dioxide is the greatest, and it is demanded to construct a method for removing carbon dioxide (for example, carbon dioxide discharged from a thermal power plant, a steelworks, and the like).
In addition, it is known that carbon dioxide affects the human body. For example, drowsiness, health damage, and the like are caused when a gas containing carbon dioxide at a high concentration is sucked. In a space with a high density of people (a building, a vehicle, or the like), the concentration of carbon dioxide (hereinafter referred to as the “CO2 concentration” in some cases) in the room is likely to rise due to the exhalation of people and the CO2 concentration is adjusted by ventilation in some cases.
It is required to operate an air blowing device such as a blower in order to quickly replace the indoor air with outdoor air. In addition, it is required to operate the cooling system in the summer and to operate the heating system in the winter since the temperature and humidity of the air (outdoor air) taken in from the outside are not adjusted. For these reasons, an increase in CO2 concentration in the room is a cause of an increase in power consumption associated with air conditioning.
The decrease amount of carbon dioxide (CO2 decrease amount) in the room due to ventilation is expressed by the following equation. In the following equation, the CO2 concentration can be constantly maintained when the CO2 decrease amount on the left side is equivalent to the CO2 increase amount due to the exhalation of people.
CO2 decrease amount=(CO2 concentration in room−CO2 concentration in outdoor air)×amount of ventilation
In recent years, however, the difference between CO2 concentration in the outdoor air and CO2 concentration in the room has decreased since the CO2 concentration in the outdoor air has increased. Hence, the amount of ventilation required for adjusting the CO concentration has also increased. In the future, it is considered that the power consumption for the adjustment of the CO2 concentration by ventilation will increase if the CO2 concentration in the outdoor air further increases.
The problem is caused by replacement of the indoor air with outdoor air. Hence, the amount of ventilation can be decreased if carbon dioxide can be selectively removed by a method other than ventilation, and as a result, there is a possibility that the power consumption associated with air conditioning can be decreased.
In addition, since it is difficult to replace the indoor air with outdoor air in a space (space station, submarine, or the like) shielded from the outdoor air in which air exists, it is required to selectively remove carbon dioxide by a method other than ventilation.
Examples of a solution to the above problem may include a method in which carbon dioxide is removed by a chemical absorption method, a physical absorption method, a membrane separation method, an adsorption separation method, a cryogenic separation method, or the like. Examples thereof may include a method (CO2 separation recovery method) in which carbon dioxide is separated and recovered using a CO2 adsorbent (hereinafter simply referred to as the “adsorbent”). As the adsorbent, for example, zeolite is known (see, for example, Patent Literature 1 below).
Meanwhile, the method for removing carbon dioxide using an adsorbent is demanded to improve the amount of carbon dioxide adsorbed on the adsorbent from the viewpoint of improving the removal efficiency of carbon dioxide.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adsorbent and a method for producing the same by which the adsorption amount of carbon dioxide can be improved. In addition, an object of the present invention is to provide a method for removing carbon dioxide, a device for removing carbon dioxide and an air conditioner in which the adsorbent is used.
A method for producing an adsorbent according to the present invention is a method for producing an adsorbent used for removing carbon dioxide from a gas (a gas to be a target of treatment) containing carbon dioxide, the method including a reaction step of reacting a mixture containing tetravalent cerium and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound.
According to the method for producing an adsorbent of the present invention, it is possible to obtain an adsorbent capable of improving the adsorption amount of carbon dioxide. Such an adsorbent exhibits excellent CO2 adsorptivity (carbon dioxide adsorptivity, carbon dioxide trapping ability).
Meanwhile, in the method using an adsorbent such as zeolite, the removal efficiency of carbon dioxide tends to decrease in a case in which the CO2 concentration in the gas is low. On the other hand, according to the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent in a case in which the CO2 concentration in the gas is low. According to the present invention as described above, it is possible to efficiently remove carbon dioxide in a case in which the CO2 concentration in the gas is low.
It is preferable that the mixture is a mixture of at least one kind selected from the group consisting of cerium(IV) hydroxide, ammonium cerium(IV) nitrate and ammonium cerium(IV) sulfate with at least one kind selected from the group consisting of urea, a urea derivative and an amide compound.
The mixture may further contain a rare earth element other than cerium.
The method for producing an adsorbent according to the present invention may further include a step of obtaining the tetravalent cerium by oxidizing trivalent cerium.
In the method for producing an adsorbent according to the present invention, the mixture may be maintained at a temperature of 25° C. more in the reaction step.
The method for producing an adsorbent according to the present invention may further include a step of mixing the mixture with a base.
A first embodiment of an adsorbent according to the present invention is an adsorbent obtained by the method for producing an adsorbent described above. A second embodiment of an adsorbent according to the present invention is an adsorbent used for removing carbon dioxide from a gas containing carbon dioxide, which has a structure derived by a reaction of a mixture containing tetravalent cerium and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound.
A method for removing carbon dioxide according to the present invention includes a step of bringing an adsorbent obtained by the method for producing an adsorbent described above or the adsorbent described above into contact with a gas containing carbon dioxide to adsorb carbon dioxide on the adsorbent. According to the method for removing carbon dioxide of the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent and to improve the removal efficiency of carbon dioxide.
A device for removing carbon dioxide according to the present invention contains an adsorbent obtained by the method for producing an adsorbent described above or the adsorbent described above. According to the device for removing carbon dioxide of the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent and to improve the removal efficiency of carbon dioxide.
An air conditioner according to the present invention is an air conditioner used in a space containing a gas containing carbon dioxide, the air conditioner including a flow path connected to the space, in which a removal section for removing carbon dioxide contained in the gas is disposed in the flow path, an adsorbent obtained by the method for producing an adsorbent described above or the adsorbent described above is disposed in the removal section, and the carbon dioxide adsorbs on the adsorbent as the adsorbent comes into contact with the gas. According to the air conditioner of the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent and to improve the removal efficiency of carbon dioxide.
A CO2 concentration in the gas may be 5000 ppm or less or 1000 ppm or less.
According to the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent. According to the present invention, it is possible to improve the amount of carbon dioxide adsorbed on the adsorbent particularly in a case in which the CO2 concentration in the gas is low. According to the present invention, it is possible to provide use of an adsorbent to the removal of carbon dioxide from a gas containing carbon dioxide.
In the present specification, the numerical range expressed by using “to” indicates the range including the numerical values stated before and after “to” as the minimum value and the maximum value, respectively. In a numerical range stated in a stepwise manner in the present specification, the upper limit value or lower limit value in the numerical range at a certain stage may be replaced with the upper limit value or lower limit value in the numerical range at another stage. In addition, in a numerical range stated in the present specification, the upper limit value or lower limit value in the numerical range may be replaced with the values stated in Examples.
In the present specification, the term “step” includes not only an independent step but also a step by which the intended purpose of the step can be achieved even in a case in which the step cannot be clearly distinguished from other steps. The materials exemplified in the present specification can be used singly or in combination of two or more kinds thereof unless otherwise stated. In the present specification, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise stated in a case in which a plurality of substances corresponding to each component are present in the composition.
Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
<Method for Producing Adsorbent>
The method for producing an adsorbent according to the present embodiment is a method for producing an adsorbent used for removing (for example, recovering) carbon dioxide from a gas containing carbon dioxide. At least a part of carbon dioxide contained in the gas may be removed using the adsorbent. The method for producing an adsorbent according to the present embodiment includes a reaction step of reacting a mixture containing tetravalent cerium (for example, a tetravalent cerium ion) and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound. In the reaction step, it is possible to obtain a reaction product (precipitate) containing cerium oxide (cerium oxide particles and the like) by the reaction of tetravalent cerium with at least one kind selected from the group consisting of urea, a urea derivative and an amide compound. The reaction product containing cerium oxide may further contain a hydroxide of cerium.
As a result of intensive investigations, the inventors of the present invention have found out that an adsorbent obtained by reacting a mixture containing tetravalent cerium and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound exhibits excellent CO2 adsorptivity. The reason why such an effect is obtained is not clear, but the inventors of the present invention presume as follows. In the method for producing an adsorbent according to the present embodiment, the pH of the mixture (solution or the like) gently increases as urea, a urea derivative or an amide compound is gradually hydrolyzed in the mixture containing water by use of urea, a urea derivative or an amide compound. It is presumed that an adsorbent having pores profitable for trapping of CO2 is obtained since a homogeneous and fine reaction product is generated by this. According to the method for producing an adsorbent of the present embodiment, an adsorbent is obtained which exhibits excellent CO2 adsorptivity particularly in a case in which the CO2 concentration in the gas is low.
The pH (for example, the pH at the end of the reaction) of the mixture is preferably 4 or more and more preferably 5 or more from the viewpoint that a reaction product is likely to be generated. The pH of the mixture is preferably 9 or less, more preferably 7 or less, still more preferably less than 7, and particularly preferably 6 or less from the viewpoint that a reaction product is likely to be generated. The pH of the mixture is, for example, the pH at the end of the reaction. The hydrolysis rate varies depending on the kind and blended amount of the compound (urea, a urea derivative, an amide compound or the like) to react with tetravalent cerium, the reaction temperature and the like, and by adjusting these, the particle size and the like of the reaction product can be adjusted.
Examples of the urea derivative may include N-monoalkylurea, N,N-dialkylurea, N,N′-dialkylurea, N-allylurea, diacetylurea, benzoylurea, phenylsulfonylurea, p-tolylsulfonylurea, trialkylurea, tetraalkylurea, N-monophenylurea, N,N-diphenylurea, N,N′-diphenylurea, N-(4-ethoxyphenyl)-N′-vinylurea, nitrosourea, biurea, biuret, guanylurea, hydantoin, a urea derivative having a silicon atom, other ureido compounds, isourea, isourea derivatives, and semicarbazide compounds. One kind of urea derivative may be used singly or two or more kind thereof may be used in combination.
The amide compound is a compound (excluding urea and a urea derivative) having at least one amide bond in the molecule. As the amide compound, carboxylic acid amide and N,N-dimethylformamide can be used. One kind of amide compound may be used singly or two or more kinds thereof may be used in combination.
In the reaction step, the mixture may be maintained at the following reaction temperature. The reaction temperature is preferably 25° C. more, more preferably 60° C. to 100° C., and still more preferably 80° C. to 95° C. from the viewpoint that a homogeneous reaction product containing cerium oxide is likely to be obtained (for example, a suitable hydrolysis rate is likely to be obtained). The time maintained at the reaction temperature may be, for example, 10 hours or less or 4 hours or less.
Tetravalent cerium can be supplied by using a compound containing tetravalent cerium. Examples of the compound containing tetravalent cerium may include cerium(IV) oxide, cerium(IV) hydroxide, cerium(IV) nitrate, ammonium cerium(IV) nitrate, ammonium cerium(IV) sulfate, and hydrates thereof. As the compound containing tetravalent cerium, at least one kind selected from the group consisting of cerium(IV) hydroxide, ammonium cerium(IV) nitrate and ammonium cerium(IV) sulfate is preferable from the viewpoint that a reaction product containing cerium oxide is likely to be obtained. In other words, it is preferable that the mixture in the reaction step is a mixture of at least one kind selected from the group consisting of cerium(IV) hydroxide, ammonium cerium(IV) nitrate and ammonium cerium(IV) sulfate with at least one kind selected from the group consisting of urea, a urea derivative and an amide compound. One kind of compound containing tetravalent cerium may be used singly or two or more kinds thereof may be used in combination.
The amount of the compound containing tetravalent cerium. blended is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the sum of urea, a urea derivative and an amide compound from the viewpoint that a reaction product containing cerium oxide is likely to be obtained. The amount of the compound containing tetravalent cerium blended is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less with respect to 100 parts by mass of the sum of urea, a urea derivative and an amide compound from the viewpoint that a reaction product containing cerium oxide is likely to be obtained. From these viewpoints, the amount of the compound containing tetravalent cerium blended is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 50 parts by mass, and still more preferably 20 parts by mass to 30 parts by mass with respect to 100 parts by mass of the sum of urea, a urea derivative and an amide compound.
Tetravalent cerium can also be supplied by oxidizing trivalent cerium (for example, a trivalent cerium ion). In other words, the method for producing an adsorbent according to the present embodiment can further include a step of obtaining tetravalent cerium by oxidizing trivalent cerium. Trivalent cerium can be supplied by using a compound containing trivalent cerium. The compound containing tetravalent cerium can be obtained by oxidizing a compound containing trivalent cerium. For example, a compound containing tetravalent cerium (hydroxide of tetravalent cerium or the like) can be obtained by mixing a reaction product obtained by mixing a compound containing trivalent cerium and an oxidizing agent (such as hydrogen peroxide) with an acid component (nitric acid or the like).
Examples of the compound containing trivalent cerium may include cerium(III) nitrate, cerium(III) oxalate, cerium(III) acetate, cerium(II) carbonate, and hydrates thereof. The compound containing trivalent cerium can be obtained, for example, by mixing a compound containing tetravalent cerium (cerium(IV) oxide or the like), hydrogen peroxide, and an acid component (nitric acid or the like) together. One kind of compound containing trivalent cerium may be used singly or two or more kinds thereof may be used in combination.
The mixture in the reaction step may further contain a rare earth element other than cerium (for example, a rare earth ion) from the viewpoint of further improving the adsorption amount of carbon dioxide. It is presumed that the adsorption amount of carbon dioxide is further improved since the bias of charge at the composite site of cerium with a rare earth element increases and the interaction with the positive charge of carbon dioxide is strengthened as the mixture in the reaction step contains a rare earth element. The reaction product (precipitate) contains cerium oxide and a rare earth element in a case in which the mixture in the reaction step contains a rare earth element.
Examples of the rare earth element may include lanthanides (lanthanum, neodymium, praseodymium and the like) and yttrium. The rare earth element can be supplied by using a compound containing a rare earth element. Examples of the compound containing a rare earth element may include nitrates of rare earth elements such as lanthanum nitrate, neodymium nitrate, praseodymium nitrate, and yttrium nitrate, and hydrates of the nitrates. One kind of compound containing a rare earth element may be used singly or two or more kinds thereof may be used in combination.
In the mixture in the reaction step, the blended ratio (molar ratio; content of rare earth element (excluding cerium)/content of cerium) of the rare earth element (excluding cerium) to cerium is preferably 0.001 or more and more preferably 0.1 or more from the viewpoint of further improving the adsorption amount of carbon dioxide. The blended ratio is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.3 or less from the viewpoint of further improving the adsorption amount of carbon dioxide. From these viewpoints the blended ratio is preferably 0.001 to 1, more preferably 0.001 to 0.5, and still more preferably 0.1 to 0.3.
The method for producing an adsorbent according to the present embodiment may further include a step of mixing the mixture in the reaction step with a base. The generation of the reaction product is promoted since this makes it possible to promote the precipitation of the rare earth element. In addition, it is possible to remove insoluble components by separating the precipitate from the filtrate containing unwanted components (nitrate ion and the like) by filtration. A base may be mixed with the mixture over several times. Examples of the base may include ammonia and sodium hydroxide. One kind of base may be used singly or two or more kinds thereof may be used in combination.
It is possible to obtain cerium oxide by separating the reaction product (precipitate) by a method such as suction filtration or centrifugation, then washing the reaction product with water, and drying the reaction product. The reaction product may be fired (for example, 200° C. to 300° C.) after being obtained.
<Adsorbent>
The adsorbent according to the present embodiment is produced by a method including a reaction step of reacting a mixture containing tetravalent cerium and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound. The adsorbent according to the present embodiment has a structure derived by the reaction of a mixture containing tetravalent cerium and at least one kind selected from the group consisting of urea, a urea derivative and an amide compound. The adsorbent (carbon dioxide trapping agent) according to the present embodiment is used for removing carbon dioxide from a gas containing carbon dioxide.
The adsorbent according to the present embodiment may be an adsorbent produced by a method including a reaction step of reacting a mixture containing tetravalent cerium, at least one kind selected from the group consisting of urea, a urea derivative and an amide compound, and a rare earth element other than cerium. Such an adsorbent has a structure derived by the reaction of a mixture containing tetravalent cerium, at least one kind selected from the group consisting of urea, a urea derivative and an amide compound, and a rare earth element other than cerium.
The adsorbent according to the present embodiment can contain cerium oxide. Examples of cerium oxide may include CeOx (x=1.5 to 2.0), and specific examples thereof may include CeO2 and Ce2O3. The adsorbent according to the present embodiment may contain a rare earth element. The rare earth element may be contained, for example, as an oxide, a hydroxide, or the like.
The adsorbent may be chemically treated. For example, the specific surface area of the adsorbent may be increased by being mixed with a filler (alumina, silica, or the like) as a binder.
The content of cerium oxide in the adsorbent may be 30% by mass or more, 70% by mass or more, or 90% by mass or more based on the total mass of the adsorbent. The adsorbent may consist of cerium oxide (the content of cerium oxide may be substantially 100% by mass based on the total mass of the adsorbent). The adsorption amount of carbon dioxide can be further improved as the content of cerium oxide increases. The content of cerium oxide can be adjusted by, for example, the content of a tetravalent cerium in the mixture.
Examples of the shape of the adsorbent may include a powdery shape, a pellet shape, a granular shape, and a honeycomb shape. The shape of the adsorbent may be determined in consideration of the required reaction rate, pressure loss, amount adsorbed on the adsorbent, purity (CO2 purity) of the gas (adsorbed gas) to adsorb on the adsorbent, and the like.
<Method for Removing Carbon Dioxide>
The method for removing carbon dioxide according to the present embodiment includes an adsorption step of bringing the adsorbent according to the present embodiment into contact with a gas containing carbon dioxide to adsorb carbon dioxide on the adsorbent.
The CO2 concentration in the gas may be 5000 ppm or less (0.5% by volume or less) based on the total volume of the gas. According to the method for removing carbon dioxide of the present embodiment, carbon dioxide can be efficiently removed in a case in which the CO2 concentration is 5000 ppm or less. The reason why such an effect is exerted is not clear, but the inventors of the present invention presume as follows. It is considered that carbon dioxide adsorbs on the adsorbent as carbon dioxide does not physically adsorb on the surface of cerium oxide but chemically bonds to the surface of cerium oxide in the adsorption step. In this case, in the method for removing carbon dioxide according to the present embodiment, it is presumed that the partial pressure dependency of carbon dioxide at the time of adsorption on the adsorbent is minor and thus carbon dioxide can be efficiently removed even when the CO2 concentration in the gas is 5000 ppm or less.
From the viewpoint that the effect of efficiently removing carbon dioxide is likely to be confirmed even in a case in which the CO2 concentration is low, the CO2 concentration may be 2000 ppm or less, 1500 ppm or less, 1000 ppm or less, 750 ppm or less, or 500 ppm or less based on the total volume of the gas. From the viewpoint that the amount of carbon dioxide removed is likely to increase, the CO2 concentration may be 100 ppm or more, 200 ppm or more, or 400 ppm or more based on the total volume of the gas. From these viewpoints, the CO2 concentration may be 100 ppm to 5000 ppm, 100 ppm to 2000 ppm, 100 ppm to 1500 ppm, 100 ppm to 1000 ppm, 200 ppm to 1000 ppm, 400 ppm to 1000 ppm, 400 ppm to 750 ppm, or 400 ppm to 500 ppm based on the total volume of the gas. Incidentally, it is stipulated in the Ordinance on Health Standards in Office of the Occupational Safety and Health Act that the CO2 concentration in the room should be adjusted to 5000 ppm or less. In addition, it is known that drowsiness is induced in a case in which the CO2 concentration exceeds 1000 ppm and it is stipulated in the Management Standard of Environmental Sanitation for Buildings that the CO2 concentration should be adjusted to 1000 ppm or less. Hence, there is a case in which the CO2 concentration is adjusted by ventilation so as not to exceed 5000 ppm or 1000 ppm. The CO2 concentration in the gas is not limited to the above range, and it may be 500 ppm to 5000 ppm or 750 ppm to 5000 ppm.
The gas is not particularly limited as long as it is a gas containing carbon dioxide, and it may contain a gas component other than carbon dioxide. Examples of the gas component other than carbon dioxide may include water (water vapor, H2O), oxygen (O), nitrogen (N2), carbon monoxide (CO), SOx, NOx, and volatile organic compounds (VOC). Specific examples of the gas may include air in the room of a building, a vehicle, and the like. In the adsorption step, in a case in which the gas contains water, carbon monoxide, SOx, NOx, volatile organic compounds, and the like, these gas components adsorb on the adsorbent in some cases.
Meanwhile, the CO2 adsorptivity of an adsorbent such as zeolite tends to significantly decrease in a case in which the gas contains water. Hence, in order to improve the CO2 adsorptivity of the adsorbent in the method using an adsorbent such as zeolite, it is required to perform a dehumidifying step of removing moisture from the gas before bringing the gas into contact with the adsorbent. The dehumidifying step is performed by using, for example, a dehumidifying device, and this thus leads to an increase in facility and an increase in energy consumption. On the other hand, the adsorbent according to the present embodiment exhibits superior CO2 adsorptivity even in a case in which the gas contains water. Hence, in the method for removing carbon dioxide according to the present embodiment, the dehumidifying step is not required and carbon dioxide can be efficiently removed even in a case in which the gas contains water.
The dew point of the gas may be 0° C. or more. From the viewpoint of increasing the hydroxyl groups on the surface of cerium oxide and enhancing the reactivity with CO2, the dew point of the gas may be −40° C. or more and 50° C. or less, 0° C. or more and 40° C. or less, or 10° C. or more and 30° C. or less.
The relative humidity of the gas may be 0% or more, 30% or more, 50% or more, or 80% or more. The relative humidity of the gas is preferably 100% or less (that is, dew does not condense on the adsorbent), more preferably 0.1% or more and 90% or less, and still more preferably 10% or more and 80% or less from the viewpoint of decreasing the energy consumption due to dehumidification. The above relative humidity is a relative humidity at 30° C., for example.
The adsorption amount of carbon dioxide can be adjusted by adjusting the temperature T1 of the adsorbent when bringing the gas into contact with the adsorbent in the adsorption step. The amount of CO2 adsorbed on the adsorbent tends to decrease as the temperature T1 is higher. The temperature T1 may be −20° C. to 100° C. or 10° C. to 40° C.
The temperature T1 of the adsorbent may be adjusted by heating or cooling the adsorbent, and heating and cooling may be used in combination. In addition, the temperature T1 of the adsorbent may be indirectly adjusted by heating or cooling the gas. Examples of a method for heating the adsorbent may include: a method in which a heat medium (for example, a heated gas or liquid) is brought into direct contact with the adsorbent; a method in which a heat medium (for example, a heated gas or liquid) is circulated through a heat transfer pipe or the like and the adsorbent is heated by heat conduction from the heat transfer surface; and a method in which the adsorbent is heated by using an electric furnace which has been electrically heated or the like. Examples of a method for cooling the adsorbent may include: a method in which a refrigerant (for example, a cooled gas or liquid) is brought into direct contact with the adsorbent; and a method in which a refrigerant (for example, a cooled gas or liquid) is circulated through a heat transfer pipe or the like and the adsorbent is cooled by heat conduction from the heat transfer surface.
In the adsorption step, the adsorption amount of carbon dioxide can be adjusted by adjusting the total pressure (for example, the total pressure in the vessel containing the adsorbent) of the atmosphere in which the adsorbent is present. The amount of CO2 adsorbed on the adsorbent tends to increase as the total pressure is higher. The total pressure is preferably 0.1 atm or more and more preferably 1 atm or more from the viewpoint of further improving the removal efficiency of carbon dioxide. The total pressure may be 10 atm or less, 2 atm or less, or 1.3 atm or less from the viewpoint of energy saving. The total pressure may be 5 atm or more.
The total pressure of the atmosphere in which the adsorbent is present may be adjusted by pressurization or depressurization, and pressurization and depressurization may be used in combination. Examples of a method for adjusting the total pressure may include: a method in which the pressure is mechanically adjusted by using a pump, a compressor or the like; and a method in which of a gas having a pressure different from the pressure of the atmosphere surrounding the adsorbent is introduced.
In the method for removing carbon dioxide according to the present embodiment, the adsorbent may be used by being supported on a honeycomb-shaped substrate or by being filled in a vessel. The method for using the adsorbent may be determined in consideration of the required reaction rate, pressure loss, amount adsorbed on the adsorbent, purity (CO2 purity) of the gas (adsorbed gas) to adsorb on the adsorbent, and the like.
In the case of using the adsorbent by being filled in a vessel, it is more preferable as the void fraction is smaller in the case of increasing the purity of carbon dioxide in the adsorbed gas. In this case, the amount of gas remaining in the voids other than carbon dioxide decreases and thus the purity of carbon dioxide in the adsorbed gas can be increased. On the other hand, it is more preferable as the void fraction is greater in the case of diminishing the pressure loss.
The method for removing carbon dioxide according to the present embodiment may further include a desorption step of desorbing (detaching) carbon dioxide from the adsorbent after the adsorption step.
Examples of a method for desorbing carbon dioxide from the adsorbent may include: a method utilizing the temperature dependency of the adsorption amount (temperature swing method. A method utilizing a difference in the amount adsorbed on the adsorbent associated with a change in temperature); a method utilizing the pressure dependency of the adsorption amount (pressure swing method. A method utilizing a difference in the amount adsorbed on the adsorbent associated with a change in pressure), and these methods may be used in combination (temperature and pressure swing method).
In the method utilizing the temperature dependency of the adsorption amount, for example, the temperature of the adsorbent in the desorption step is set to be higher than that in the adsorption step. Examples of a method for heating the adsorbent may include: the same methods as the methods for heating the adsorbent in the adsorption step described above; and a method utilizing surrounding waste heat. It is preferable to utilize surrounding waste heat from the viewpoint of diminishing energy required for heating.
The temperature difference (T2−T1) between the temperature T1 of the adsorbent in the adsorption step and the temperature T2 of the adsorbent in the desorption step may be 200° C. or less, 100° C. or less, or 50° C. or less from the viewpoint of energy saving. The temperature difference (T2−T1) may be 10° C. or more, 20° C. or more, or 30° C. or more from the viewpoint that the carbon dioxide which has adsorbed on the adsorbent is likely to desorb. The temperature T2 of the adsorbent in the desorption step may be, for example, 40° C. to 300° C., 50° C. to 200° C., or 80° C. to 120° C.
In the method utilizing the pressure dependency of the adsorption amount, it is preferable to change total pressure so that the total pressure in the desorption step is lower than the total pressure in the adsorption step since the CO2 adsorption amount is greater as the total pressure of the atmosphere in which the adsorbent is present (for example, the total pressure in the vessel containing the adsorbent) is higher. The total pressure may be adjusted by pressurization or depressurization, and pressurization and depressurization may be used in combination. Examples of a method for adjusting the total pressure may include the same methods as those in the adsorption step described above. The total pressure in the desorption step may be the pressure of the surrounding air (for example, 1 atm) or less than 1 atm from the viewpoint of increasing the CO2 desorption amount.
The carbon dioxide desorbed and recovered through the desorption step may be discharged to the outdoor air as it is, but it may be reused in the field using carbon dioxide. For example, in greenhouse cultivation houses and the like, there is a case in which the CO2 concentration is increased to a 1000 ppm level since the growth of plants is promoted by increasing the CO2 concentration, and thus the recovered carbon dioxide may be reused for increasing the CO2 concentration.
It is preferable that the gas does not contain SOx, NOx, dust and the like since there is a possibility that the CO2 adsorptivity of the adsorbent in the adsorption step decreases in a case in which SOx, NOx, dust and the like are adsorbed on the adsorbent. In a case in which the gas contains SOx, NOx, dust and the like (for example, a case in which the gas is exhaust gas discharged from a coal fired power plant or the like), it is preferable that the method for removing carbon dioxide according to the present embodiment further includes an impurity removing step of removing impurities such as SOx, NOx, and dust from the gas before the adsorption step from the viewpoint that the CO2 adsorptivity of the adsorbent is likely to be maintained. The impurity removing step can be performed by using a removal apparatus such as a denitrification apparatus, a desulfurization apparatus, or a dust removing apparatus, and the gas can be brought into contact with the adsorbent on the downstream side of these apparatuses. In addition, in a case in which impurities such as SOx, NOx, dust and the like are adsorbed on the adsorbent, impurities adsorbed on the adsorbent can be removed by heating the adsorbent in addition to exchange of the adsorbent.
The adsorbent after being subjected to the desorption step can be used again in the adsorption step. In the method for removing carbon dioxide according to the present embodiment, the adsorption step and the desorption step may be repeatedly performed after the desorption step. The adsorbent may be cooled by the method described above and used in the adsorption step in a case in which the adsorbent is heated in the desorption step. The adsorbent may be cooled by bringing a gas containing carbon dioxide (for example, a gas containing carbon dioxide) into contact with the adsorbent.
The method for removing carbon dioxide according to the present embodiment can be suitably implemented in a sealed space which requires management of CO2 concentration. Examples of the space which requires management of CO2 concentration may include a building; a vehicle; an automobile; a space station; a submarine; a manufacturing plant for a food or a chemical product. The method for removing carbon dioxide according to the present embodiment can be suitably implemented particularly in a space (for example, a space with a high density of people such as a building and a vehicle) in which the CO2 concentration is limited to 5000 ppm or less. In addition, the method for removing carbon dioxide according to the present embodiment can be suitably implemented in a manufacturing plant for a food or a chemical product and the like since there is a possibility that carbon dioxide adversely affects at the time of manufacture of a food or a chemical product.
<Device for Removing Carbon Dioxide, Apparatus for Removing Carbon Dioxide and System for Removing Carbon Dioxide>
The device for removing carbon dioxide according to the present embodiment is equipped with the adsorbent according to the present embodiment. The apparatus for removing carbon dioxide according to the present embodiment is equipped with the device (reaction vessel) for removing carbon dioxide according to the present embodiment. The apparatus for removing carbon dioxide according to the present embodiment is, for example, an air conditioner used in a space containing a gas containing carbon dioxide. The air conditioner according to the present embodiment is equipped with a flow path connected to the space, and a removal section (a device for removing carbon dioxide, a carbon dioxide removing section) for removing carbon dioxide contained in the gas is disposed in the flow path. In the air conditioner according to the present embodiment, the adsorbent according to the present embodiment is disposed in the removal section, and carbon dioxide adsorbs on the adsorbent as the adsorbent comes into contact with the gas. According to the present embodiment, there is provided an air conditioning method including an adsorption step of bringing a gas in a space to be air-conditioned into contact with an adsorbent to adsorb carbon dioxide on the adsorbent. Incidentally, the details of the gas containing carbon dioxide are the same as those of the gas in the method for removing carbon dioxide described above. Hereinafter, an air conditioner will be described as an example of an apparatus for removing carbon dioxide with reference to
As illustrated in
The flow path 10 is connected to a space R to be air-conditioned containing a gas (indoor gas) containing carbon dioxide. The flow path 10 includes a flow path section 10a, a flow path section 10b, a removal section (a flow path section, a carbon dioxide removing section) 10c, a flow path section 10d, a flow path section (circulation flow path) 10e, and a flow path section (exhaust flow path) 10f, and the removal section 10c is disposed in the flow path 10. The air conditioner 100 is equipped with the removal section 10c as a device for removing carbon dioxide. In the flow path 10, a valve 70a for adjusting the presence or absence of inflow of the gas in the removal section 10c and a valve 70b for adjusting the flow direction of the gas are disposed.
The upstream end of the flow path section 10a is connected to the space R and the downstream end of the flow path section 10a is connected to the upstream end of the flow path section 10b via the valve 70a. The upstream end of the removal section 10c is connected to the downstream end of the flow path section 10b. The downstream end of the removal section 10c is connected to the upstream end of the flow path section 10d. The downstream side of the flow path section 10d in the flow path 10 is branched into the flow path section 10e and the flow path section 10f. The downstream end of the flow path section 10d is connected to the upstream end of the flow path section 10e and the upstream end of the flow path section 10f via the valve 70b. The downstream end of the flow path section 10e is connected to the space R. The downstream end of the flow path section 10f is connected to the outdoor air.
An adsorbent 80 which is the adsorbent according to the present embodiment is disposed in the removal section 10c. The adsorbent 80 is filled in the central portion of the removal section 10c. Two spaces are formed in the removal section 10c via the adsorbent 80, and the removal section 10c includes a space S1 on the upstream side, a central portion S2 filled with the adsorbent 80, and a space S3 on the downstream side. The space S1 is connected to the space R via the flow path sections 10a and 10b and the valve 70a, and the gas containing carbon dioxide is supplied from the space R to the space S of the removal section 10c. The gas which has been supplied to the removal section 10c moves from the space S1 to the space S3 through the central portion S2 and then is discharged from the removal section 10c.
At least a part of carbon dioxide in the gas which has been discharged from the space R is removed in the removal section 10c. The gas from which carbon dioxide has been removed may be returned to the space R by adjusting the valve 70b or discharged to the outdoor air present outside the air conditioner 100. For example, the gas which has been discharged from the space R can flow into the space R from the upstream to the downstream through the flow path section 10a, the flow path section 10b, the removal section 10c, the flow path section 10d, and the flow path section 10e. In addition, the gas which has been discharged from the space R may be discharged to the outdoor air from the upstream to the downstream through the flow path section 10a, the flow path section 10b, the removal section 10c, the flow path section 10d, and the flow path section 10f.
The exhaust fan 20 is disposed at the discharge position of the gas in the space R. The exhaust fan 20 discharges the gas from the space R and supplies the gas to the removal section 10c.
The device for measuring concentration 30 measures the concentration of carbon dioxide in the space R. The device for measuring concentration 30 is disposed in the space R.
The electric furnace 40 is disposed outside the removal section 10c of the air conditioner 100 and can raise the temperature of the adsorbent 80. The compressor 50 is connected to the removal section 10c of the air conditioner 100 and can adjust the pressure inside the removal section 10c.
The control apparatus 60 can control the operation of the air conditioner 100, and for example, it can control the presence or absence of inflow of the gas in the removal section 10c based on the concentration of carbon dioxide measured by the device for measuring concentration 30. More specifically, the concentration information is transmitted from the device for measuring concentration 30 to the control apparatus 60 in a case in which the device for measuring concentration 30 detects that the concentration of carbon dioxide in the space R has increased by exhalation or the like and reached a predetermined concentration. The control apparatus 60, which has received the concentration information, opens the valve 70a and also adjusts so that the gas discharged from the removal section 10c flows into the space R via the flow path section 10d and the flow path section 10e. Thereafter, the control apparatus 60 operates the exhaust fan 20 to supply the gas from the space R to the removal section 10c. Furthermore, the control apparatus 60 operates the electric furnace 40 and/or the compressor 50 if necessary to adjust the temperature of the adsorbent 80, the pressure in the removal section 10c, and the like.
The gas comes into contact with the adsorbent 80 and carbon dioxide in the gas adsorbs on the adsorbent 80 as the gas supplied to the removal section 10c moves from the space S1 to the space S3 via the central portion S2. By this, carbon dioxide is removed from the gas. In this case, the gas from which carbon dioxide has been removed is supplied to the space R via the flow path section 10d and the flow path section 10e.
Carbon dioxide adsorbed on the adsorbent 80 may be recovered in a state of being adsorbed on the adsorbent 80 without being desorbed from the adsorbent 80 or may be desorbed from the adsorbent 80 and recovered. In the desorption step, carbon dioxide can be desorbed from the adsorbent 80 by the temperature swing method, pressure swing method and the like described above as the temperature of the adsorbent 80, the pressure inside the removal section 10c, and the like are adjusted by operating the electric furnace 40 and/or the compressor 50. In this case, for example, the valve 70b is adjusted so that the gas (gas containing the desorbed carbon dioxide) discharged from the removal section 10c is discharged to the outdoor air via the flow path section 10f, and discharged carbon dioxide can be recovered if necessary.
The system for removing carbon dioxide according to the present embodiment is equipped with a plurality of apparatuses for removing carbon dioxide according to the present embodiment. The system for removing carbon dioxide according to the present embodiment is, for example, an air conditioning system equipped with a plurality of air conditioners according to the present embodiment. The system for removing carbon dioxide according to the present embodiment may be equipped with a control section for controlling the operation of a plurality of apparatuses for removing carbon dioxide (for example, air conditioning operation of the air conditioner). For example, the system for removing carbon dioxide according to the present embodiment comprehensively controls the operation of a plurality of apparatuses for removing carbon dioxide (for example, the air conditioning operation of the air conditioner). Hereinafter, an air conditioning system will be described as an example of the system for removing carbon dioxide with reference to
As illustrated in
The device for removing carbon dioxide, the apparatus for removing carbon dioxide (air conditioner or the like), and the system for removing carbon dioxide (air conditioning system or the like) are not limited to the above embodiment and may be appropriately changed without departing from the gist thereof. For example, the device for removing carbon dioxide, the apparatus for removing carbon dioxide, and the system for removing carbon dioxide are not limited to being used for air conditioning but can be used in all applications for removing carbon dioxide from a gas containing carbon dioxide.
In the air conditioner, the adsorbent may be disposed in the removal section, and the adsorbent may be disposed in a part of the inner wall surface without being filled in the central portion of the removal section. The contents of control by the control section of the air conditioner are not limited to control of the presence or absence of inflow of the gas in the removal section, and the control section may adjust the inflow amount of the gas in the removal section.
In the air conditioner, a gas may be supplied to the carbon dioxide removing section by using a blower instead of the exhaust fan, and the exhaust means may not be used in a case in which the gas is supplied to the carbon dioxide removing section by natural convection. In addition, the temperature control means and the pressure control means are not limited to the electric furnace and the compressor, and various means described in the adsorption step and the desorption step can be used. The temperature control means is not limited to the heating means, and it may be a cooling means.
In the air conditioner, each of the space to be air-conditioned, the carbon dioxide removing section, the exhaust means, the temperature control means, the pressure control means, the concentration measuring section, the control apparatus, and the like is not limited to one, and a plurality of these may be disposed. The air conditioner may be equipped with a humidity adjuster for adjusting the dew point and relative humidity of the gas; a humidity measuring device for measuring the humidity of the space to be air-conditioned; a removal apparatus such as a denitrification apparatus, a desulfurization apparatus, or a dust removing apparatus.
Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
<Preparation of Adsorbent>
Into a beaker, 150 mL of pure water and 40.0 g of urea were added, and the mixture was stirred until to be uniform. Next, 10.97 g of ammonium cerium(IV) nitrate was added thereto, and the mixture was stirred at 30° C. for 10 minutes. Thereafter, the temperature of the mixture was raised to 90° C. over 30 minutes while continuously performing stirring, and the temperature was maintained at 90° C. for 3 hours. At this time, precipitation occurred in about 1 hour after the temperature reached 90° C. The pH when the precipitation occurred was 5 to 6. The solution was cooled to room temperature (25° C.), and then 1 mL of 30% by mass ammonia aqueous solution was added to the solution while stirring the solution. Thereafter, the solid was separated by suction filtration and then washed with water. Thereafter, the washed solid was dried at 120° C. for 1 hour, thereby obtaining a yellowish-white powder (adsorbent).
A greenish-white powder (adsorbent) was obtained in the same manner as in Example 1 except that 10.97 g of ammonium cerium(IV) nitrate was added to the mixture, the mixture was stirred at 30° C. for 10 minutes, then 1.75 g of neodymium nitrate hexahydrate was added thereto, and the mixture was stirred at 30° C. for 10 minutes at the stage before the temperature was raised to 90° C.
According to the following procedure, 15 g of cerium oxalate (Ce2(C2O4)3) was fired in the air. First, the temperature of cerium oxalate was raised to 120° C. at 5° C./min by using an electric furnace and then maintained at 120° C. for 1 hour. Thereafter, the temperature was raised to 300° C. at 5° C./min and then maintained at 300° C. for 1 hour. By this, a yellowish-white powder (adsorbent) was obtained.
A yellowish-white powder (adsorbent) was obtained in the same manner as in Comparative Example 1 except that cerium hydroxide (Ce(OH)4) was used instead of cerium oxalate.
First, the adsorbent was pelletized at 200 kgf by using a pressing machine and a mold having a diameter of 40 mm. Subsequently, the pellet was pulverized and then sized into a granular shape (particle size: 0.5 mm to 1.0 mm) by using a sieve. Thereafter, the adsorbent was weighed by 1.0 mL by using a measuring cylinder and fixed in a reaction tube made of quartz glass.
Subsequently, as a pretreatment, the temperature of the adsorbent was raised to 200° C. by using an electric furnace while circulating helium (He) through the reaction tube at 150 mL/min and then maintained at 200° C. for 1 hour. By this, the impurities and the gases adsorbed on the adsorbent were removed.
Subsequently, the adsorbent was cooled to a temperature of 50° C., and then the CO2 adsorption amount was measured by a CO2 pulse adsorption test while maintaining the temperature of the adsorbent at 50° C. by using an electric furnace. Specifically, the CO2 pulse adsorption test was performed by the following method. The results are illustrated in
[CO2 Pulse Adsorption Test]
As a sample gas, 10 mL of a mixed gas (relative humidity: 0%) containing CO2 at 12% by volume and He at 88% by volume was used. The sample gas was introduced in a pulse form for 2 minutes every 4 minutes. At this time, the total pressure inside the reaction tube was adjusted to 1 atm. Subsequently, the CO2 concentration at the outlet of the reaction tube was measured by gas chromatography (carrier gas: He). Introduction of the sample gas was continuously performed until the CO2 concentration measured at the outlet of the reaction tube was saturated. The CO2 adsorption amount (unit: g/L) was determined from the amount (unit: g) of carbon dioxide adsorbed until the CO2 concentration was saturated.
<Experiment B: Adsorption Desorption Test of Carbon Dioxide>
The CO2 desorption amount at each temperature was measured using the adsorbent of Example 2 by the temperature programmed desorption measurement (TPD) according to the following procedure.
First, the adsorbent was pelletized at 500 kgf by using a pressing machine and a mold having a diameter of 40 mm. Subsequently, the pellet was pulverized and then adjusted into a granular shape (particle size: 0.5 mm to 1.0 mm) by using a sieve. Thereafter, the adsorbent was weighed by 1.0 mL and fixed in a reaction tube. Subsequently, the adsorbent was dried at 120° C. in the air.
Subsequently, as the adsorption step, a mixed gas containing CO2 at 800 ppm, He (balance gas), and moisture (H2O) at 2.3% by volume was circulated through the reaction tube at a flow rate of 60 cm3/min (total pressure in the reaction tube: 1 atm) while adjusting the temperature of the adsorbent to 20° C. Incidentally, moisture was introduced by circulating the gas through a bubbler. The CO2 concentration in the outlet gas of the reaction tube was analyzed by gas chromatography and the mixed gas was circulated until adsorption saturation was achieved.
Subsequently, as a desorption step, the temperature of the adsorbent was raised from 20° C. to 200° C. at 2° C./min by using an electric furnace (total pressure in the reaction tube: 1 atm) while circulating the same mixed gas as that in the adsorption step through the reaction tube at a flow rate of 60 cm3/min as a circulating gas. The CO2 concentration in the outlet gas of the reaction tube was measured and the CO2 desorption amount (CO2 concentration in the outlet gas −800 ppm) was calculated. The CO2 desorption amount was calculated by excluding the CO2 concentration in the mixed gas from the CO2 concentration in the outlet gas. The measurement results are illustrated in
As illustrated in
1: air conditioning system, 10: flow path, 10a, 10b, 10d, 10e, 10f: flow path section, 10c: removal section (device for removing carbon dioxide), 20: exhaust fan, 30: device for measuring concentration (concentration measuring section), 40: electric furnace, 50: compressor, 60, 62: control apparatus (control section), 70a, 70b: valve, 80: adsorbent, 100, 100a, 100b: air conditioner, R: space to be air-conditioned, S1, S3: space, S2: central portion.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-129064 | Jun 2016 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/018231 | 5/15/2017 | WO | 00 |
