JP2004248565A - Apparatus for supplying carbon dioxide and warm water to greenhouse - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently supply carbon dioxide and warm water from one apparatus to a greenhouse. <P>SOLUTION: The apparatus for supplying carbon dioxide and warm water to the greenhouse is equipped with a reactor 212 charged with a catalyst for promoting reforming reaction for reacting a carbon-containing fuel with steam to form carbon dioxide and hydrogen and a carbon dioxide absorbent for reversibly absorbing and releasing formed carbon dioxide. The apparatus is equipped with a means for introducing the carbon-containing fuel and steam to the reactor 212. The apparatus is equipped with a burner 212a for oxidizing at least either of a part of a reformed fuel obtained by the reforming reaction or the carbon-containing fuel with an oxidizing agent to give generated gas and heating the carbon dioxide absorbent to a regeneration temperature and a heat exchanger 216 for cooling carbon dioxide obtained by the reforming reaction by cooling water to give the cooling water heated by carbon dioxide, supplying the cooling water as warm water to the greenhouse and carbon dioxide obtained by the reforming reaction to the greenhouse. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an apparatus for supplying carbon dioxide and hot water to a greenhouse, and more particularly, to a carbon dioxide obtained based on a fuel reforming reaction in which carbon-containing fuel and steam react with each other to produce carbon dioxide and hydrogen. And a supply device for supplying hot water to a greenhouse.
[0002]
[Prior art]
The supply of carbon dioxide, that is, carbon dioxide, is essential for plant cultivation in a greenhouse. At present, there are two main methods for supplying carbon dioxide to a greenhouse. The first method is a method in which carbon dioxide is produced by a commercially available carbon dioxide generator, and the produced carbon dioxide is supplied to a greenhouse. The second method is to purchase carbon dioxide itself and supply it to a greenhouse, which is widely used by some horticultural farmers.
[0003]
On the other hand, not only carbon dioxide but also water is required for plant cultivation, and water is supplied to the greenhouse at an appropriate temperature and amount by a commercially available water supply device.
[0004]
[Patent Document 1]
Japanese Patent Application No. 2002-16928 (filed on January 25, 2002)
[0005]
[Problems to be solved by the invention]
As described above, conventionally, the supply of carbon dioxide gas and water must be performed by another method. However, if both the carbon dioxide generator and the water supply device are purchased and installed in a greenhouse with limited space, there is a problem that the plant cultivation area is reduced.
[0006]
Although it is possible to purchase carbon dioxide without purchasing a carbon dioxide generator, in this case, it is necessary to purchase carbon dioxide every time it is needed, which is problematic.
[0007]
The present invention has been made in view of such circumstances, and provides a carbon dioxide and hot water supply device for a greenhouse that can efficiently supply carbon dioxide and hot water to a greenhouse with one device. With the goal.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the present invention employs the following means using the technology according to Patent Document 1 described above.
[0009]
That is, the invention of claim 1 is a supply device which obtains a hydrogen-rich reformed fuel, carbon dioxide and hot water from a carbon-containing fuel and steam, and supplies the carbon dioxide and hot water to a greenhouse. A vessel, a raw material introduction means, a heating means, a hot water supply means, and a carbon dioxide supply means.
[0010]
The reactor consists of a fuel reforming catalyst that promotes a fuel reforming reaction that produces carbon dioxide and hydrogen by reacting carbon-containing fuel with water vapor, and a carbon dioxide absorber that can reversibly absorb and release the generated carbon dioxide Material and filling. Further, the raw material introduction means introduces a carbon-containing fuel and steam into the reactor.
[0011]
The heating means oxidizes at least one of a part of the reformed fuel and the carbon-containing fuel obtained by the fuel reforming reaction with an oxidizing agent to obtain a product gas, and uses the product gas to generate a carbon dioxide absorbent at a regeneration temperature. Heat until The hot water supply means supplies cooling water heated by the carbon dioxide to the greenhouse as hot water by cooling the carbon dioxide obtained by the fuel reforming reaction with the cooling water. The carbon dioxide supply means supplies the carbon dioxide cooled by the hot water supply means to the greenhouse.
[0012]
Therefore, in the supply device according to the first aspect of the present invention, high-temperature carbon dioxide having a high carbon dioxide content can be obtained by the fuel reforming reaction. Therefore, by generating hot water using the high-temperature carbon dioxide gas as a heat source, both carbon dioxide and hot water can be generated from one device and supplied to the greenhouse.
[0013]
According to a second aspect of the present invention, in the apparatus for supplying carbon dioxide and hot water for a greenhouse according to the first aspect, the reactor is filled with a heat storage material for storing heat energy of generated gas.
[0014]
Therefore, in the supply device according to the second aspect of the present invention, by taking the above measures, the heat energy of the generated gas can be efficiently stored. As a result, it is possible to increase the efficiency of using thermal energy and efficiently generate high-temperature carbon dioxide gas.
[0015]
According to a third aspect of the present invention, in the carbon dioxide and hot water supply device for a greenhouse according to the first or second aspect of the present invention, the heat of absorption generated when the carbon dioxide absorbent absorbs carbon dioxide in the reactor is used as fuel. It is used as the reaction heat of the reforming reaction.
[0016]
Therefore, in the supply device according to the third aspect of the present invention, by taking the above measures, the fuel reforming reaction can be efficiently caused.
[0017]
According to a fourth aspect of the present invention, in the carbon dioxide and hot water supply device for a greenhouse according to any one of the first to third aspects, at least one of a part of the reformed fuel and the carbon-containing fuel is oxidized. The fuel is oxidized by an agent, and the reaction heat of the oxidation reaction is used as the reaction heat of the fuel reforming reaction.
[0018]
Therefore, in the supply device according to the fourth aspect of the present invention, by taking the above measures, the fuel reforming reaction can be efficiently caused.
[0019]
According to a fifth aspect of the present invention, in the carbon dioxide and hot water supply device for a greenhouse according to any one of the first to fourth aspects, the carbon dioxide released from the carbon dioxide absorbent is released. It has recycling means for recycling to a reactor having a carbon dioxide absorbent.
[0020]
Therefore, in the supply device according to the fifth aspect of the present invention, even if excess carbon dioxide (carbon dioxide gas) is generated with respect to the supply amount to the greenhouse by taking the above-described means, It can be used effectively by recycling carbon dioxide.
[0021]
According to a sixth aspect of the present invention, in the apparatus for supplying carbon dioxide and hot water for a greenhouse according to the fifth aspect of the present invention, the heating means heats the carbon dioxide absorbent with a mixed gas of the produced gas and the recycled carbon dioxide.
[0022]
Therefore, in the supply device according to the sixth aspect of the present invention, by taking the above measures, the recycled carbon dioxide can also be effectively used as a heat source of the heating means.
[0023]
According to a seventh aspect of the present invention, in the carbon dioxide and hot water supply apparatus for a greenhouse according to the fifth aspect, the heating means heats the carbon dioxide absorbent by indirectly heating the recycling means.
[0024]
Therefore, in the supply device according to the seventh aspect of the present invention, by taking the above measures, the recycled carbon dioxide can also be effectively used as a heat source of the heating means.
[0025]
According to an eighth aspect of the present invention, there is provided the carbon dioxide and hot water supply device for a greenhouse according to any one of the first to seventh aspects, wherein the carbon dioxide absorbent is reacted with carbon dioxide to produce a carbonate. And at least one carbonate selected from the group consisting of alkali metal carbonates and alkaline earth metal carbonates is a mixture added to the compound.
[0026]
Therefore, in the supply device according to the eighth aspect of the present invention, by taking the above measures, the carbon dioxide absorbent can efficiently absorb carbon dioxide.
[0027]
According to a ninth aspect of the present invention, in the greenhouse carbon dioxide and hot water supply apparatus according to any one of the first to eighth aspects, the compound that reacts with carbon dioxide to generate a carbonate is lithium zirconate. At least one lithium composite oxide selected from the group consisting of lithium ferrite and lithium silicate.
[0028]
In addition to being able to be used repeatedly, these composite oxides can efficiently absorb only carbon dioxide after the fuel reforming reaction, and then can extract only carbon dioxide. Moreover, since carbon dioxide is efficiently absorbed simultaneously with the reforming reaction, the fuel reforming reaction can be promoted.
[0029]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
[0030]
FIG. 1 is a process flow diagram illustrating a configuration example of a supply device according to an embodiment of the present invention.
FIG. 2 is a system configuration diagram showing a detailed configuration example around the reactor.
FIG. 3 is a typical timing chart showing an operation method of the supply device according to the embodiment of the present invention.
FIG. 4 is a timing chart showing a modification of the operation method of the supply device according to the embodiment of the present invention.
[0031]
As shown in FIG. 2, the reactor 212 used in the present invention is filled with a fuel reforming catalyst, a carbon dioxide absorbent, and a heat storage material as necessary for reducing the thermal load of the apparatus and adjusting the heat balance. You. The shape and arrangement of the fuel reforming catalyst, carbon dioxide absorbent, and heat storage material depend on the reforming reaction in which the heat stored in the carbon dioxide absorbent and heat storage material and the heat absorbed by the carbon dioxide absorbent progress in the fuel reforming catalyst. Any material can be used as long as it can be supplied and carbon dioxide generated by the fuel reforming reaction can reach and be absorbed by the carbon dioxide absorbent. For example, the fuel reforming catalyst, the carbon dioxide absorbent, and the heat storage material may be all in the form of granules, mixed, and filled so that they are in direct contact with each other to form the packed layer 212b.
[0032]
Also, the raw material powders of the respective fillers are mixed and molded into spherical, cylindrical, ring, perforated wheel, honeycomb, and corrugated (corrugated) shapes. 212b. It does not hinder the flow of gas passing through the packed bed 212b, and disperses the gas evenly in the packing material, that is, does not hinder the transfer of substances. In order to maximize the effect of the present invention, it is preferable to arrange and fill so that the heat material is in direct contact with the material and fill it so as not to hinder the transfer of heat. It may be arbitrarily selected in consideration of the above.
[0033]
In the present invention, the absorption temperature is a temperature at which the carbon dioxide absorbent can absorb carbon dioxide and means a temperature at which a fuel reforming reaction can occur. The absorption temperature is preferably 400 ° C. or higher from the viewpoint of the degree of progress of the fuel reforming reaction and the hydrogen concentration in the obtained reformed fuel, and is preferably lower than 700 ° C. from the viewpoint of carbon dioxide absorption rate. The regeneration temperature means a temperature at which the carbon dioxide absorbent can release carbon dioxide. The regeneration temperature is preferably 700 ° C. or higher from the viewpoint of the release rate of carbon dioxide. Further, in terms of the material, since the temperature of the device such as the reactor 212 or the filler such as the carbon dioxide absorbent changes repeatedly and periodically, the temperature and temperature change is preferable.
[0034]
In the present invention, since the absorption temperature and the regeneration temperature are periodically repeated (temperature swing), the design temperature of the reactor 212 itself is governed by the higher regeneration temperature, which is a feature of the packed layer 212b. Considering that the simultaneous transfer of the substance and the heat can be achieved only by randomly filling the reforming catalyst and the carbon dioxide absorbent, it is perpendicular to the gas flow direction, that is, the radial direction of the reactor 212. Has no restriction on the radial length (tube diameter) described in the conventional multitubular reactor (not shown), and the radial size (reactor diameter) is arbitrarily determined. .
[0035]
In the conventional multi-tube reactor, heat input from the outside was transferred to the packed bed through the tube wall. For this reason, a high-grade material has been required as a tube material. However, in the present invention, it is preferable that a structure in which heat does not transfer from the outside and heat inside does not escape to the outside is provided. Therefore, the inside of the reactor 212 can be lined with a refractory brick and the inside can be filled with a filler, and the outer wall of the reactor 212 can use a general-purpose structural member (a material having a low heat-resistant temperature), which is extremely economical. Configuration.
[0036]
As the carbon-containing fuel, any fuel containing carbon can be used.For example, gas containing methane, ethane, propane, etc., lower alcohols, lower ethers can be used. Natural gas, city gas, LPG, naphtha, methyl alcohol or dimethyl ether used as fuel can be used.
[0037]
In addition, the absorption capacity of carbon dioxide absorbents, such as hydrogen sulfide and sulfur dioxide, is greatly reduced when sulfur content is used.Use a carbon-containing fuel from which sulfur has been removed or desulfurize the carbon-containing fuel in the supply device. Is preferred.
[0038]
The specific material of the heat storage material is the temperature at which the reforming reaction according to the present invention proceeds, the temperature at which carbon dioxide is absorbed and released, the stability in the atmosphere, the specific heat, the thermal conductivity, the true density, the bulk density, and the economic efficiency. For example, materials such as magnesia, lithium aluminate, and zirconia can be suitably used.
[0039]
FIG. 2 shows a mode in which one reactor 212 is used, and the operation is periodically and repeatedly performed according to a typical timing chart shown in FIG. 3 to be an intermittent operation. The solid line shown in FIG. 2 is the line used in the fuel reforming / carbon dioxide separation step (step 1), the dashed line is the line used in the absorbent regeneration / heat storage step (step 2), and the broken line is the cooling / fuel reforming step. The lines used in the process (step 3) are shown. In FIG. 3, the abscissa indicates the elapsed time, the ordinate indicates the average temperature of the packed bed 212b in the reactor 212, and indicates the operation for one cycle. As will be described later, another embodiment in which the reformed fuel is continuously obtained is described later with reference to FIG. 1, and therefore, the description of FIG. 2 will be briefly described.
[0040]
First, an embodiment using one reactor 212 will be described with reference to FIG. Inside the reactor 212, a packed layer 212b filled with a fuel reforming catalyst, a carbon dioxide absorbent and, if necessary, a heat storage material is formed. The shape and arrangement of these fillers 212b have already been described. Also, for the sake of explanation, one cycle starts with a fuel reforming / carbon dioxide separation step (step 1), then an absorbent regeneration / heat storage step (step 2), and finally a cooling / fuel reforming step (step 3). I do.
[0041]
In step 1, the process starts from a state in which the average temperature of the packed bed 212b of the reactor 212 is cooled to the absorption temperature which is the temperature at the end of step 3 in the previous cycle. Although not shown in FIG. 2, a mixed gas (hereinafter, also referred to as “raw material gas” in some cases) mixed with a desulfurized carbon-containing fuel and steam and heated to a predetermined temperature passes through a line 221 and passes through a switching valve 213 a And supplied to the reactor 212. At this time, the switching valves 213b and 213c are closed. When the raw material gas passes through the packed bed 212b, it comes into contact with the reforming catalyst and the carbon dioxide absorbent, and flows toward the lower reactor outlet 217 while causing a fuel reforming reaction and a carbon dioxide absorbing reaction.
[0042]
As will be described later, the reforming reaction is endothermic, while the carbon dioxide absorption reaction is exothermic, but if these reactions occur simultaneously, it becomes a weak endothermic. Accordingly, in an adiabatic reactor having no heating source, the reaction temperature decreases toward the reactor outlet. Here, the temperature of the reaction gas passing through the switching valve 214a from the reactor outlet 217 is monitored by the thermometer 215a. Then, an oxidizing agent and a fuel (a part of the reformed fuel and / or a carbon-containing fuel) are supplied from a reactor inlet 218 provided at an upper portion of the reactor as appropriate, and the burner 212a oxidizes the fuel. Thereby, the generated oxidation reaction heat can be used as a heating source, and the average temperature of the filling layer 212b can be maintained substantially constant.
[0043]
The completion time of Step 1 can be confirmed from an elapsed time by preparing a breakthrough curve in advance from the average temperature of the packed bed 212b and the amount of the filled carbon dioxide absorbent. Alternatively, the composition of the reformed fuel gas at the reactor outlet 217 can be analyzed by an analyzer (not shown) to know the concentration of carbon dioxide that is not absorbed but breaks through. After the end of step 1, the process proceeds to step 2.
[0044]
In step 2, the reformed fuel gas remaining in the reactor 212 is discharged, and the average temperature of the packed bed 212a is raised to a regeneration temperature required for regenerating the carbon dioxide absorbent. Begin.
[0045]
When recovering the carbon dioxide absorbed by the carbon dioxide absorbent as high-purity carbon dioxide gas, it is desirable to recycle the carbon dioxide gas. Although not shown in FIG. 2, the carbon dioxide-containing gas from the gas holder storing the required amount of the carbon dioxide gas released from the carbon dioxide absorbent in step 2 passes through the line 222, the switching valve 213b, and the reactor. 212. At this time, the external heating device 211 can heat the carbon dioxide-containing gas to a predetermined regeneration temperature. Alternatively, the oxidizing agent and the fuel are supplied, the fuel is oxidized by the burner 212a, and the generated heat of the oxidation reaction is used as a heating source, and the carbon dioxide-containing gas is heated to the regeneration temperature without using the heating device 211 as in Step 1. It can also be heated.
[0046]
The heated carbon dioxide-containing gas supplied from the upper part of the reactor inlet 218 is sequentially filled with the packing (fuel reforming catalyst, carbon dioxide absorbent, and possibly heat storage) at the absorption temperature at the end of Step 1 in the flow direction. (Including materials), causing heat transfer and heating of the fill. When the temperature reaches the regeneration temperature, carbon dioxide gas is released from the carbon dioxide absorbing material that has absorbed carbon dioxide. The released carbon dioxide gas is mixed with the carbon dioxide-containing gas supplied to the reactor 212 in the reactor 212, becomes a high-temperature carbon dioxide-containing gas, passes through the switching valve 214b, passes through the heat exchanger 216, and enters the greenhouse. Supplied. Further, in the heat exchanger 216, the cooling water supplied for cooling the high-temperature carbon dioxide-containing gas is heated by the high-temperature carbon dioxide-containing gas to become hot water and supplied to the greenhouse.
[0047]
In the packed bed 212b of the reactor 212, the boundary between the regeneration temperature and the absorption temperature moves in the flow direction with time.
[0048]
The release of carbon dioxide gas from the carbon dioxide absorbent is an endothermic reaction, and the temperature decreases as it proceeds in the flow direction. Further, when the heat storage material is included, the temperature decreases in the flow direction in order to supply the sensible heat of the heat storage material itself, and the temperature required for regeneration cannot be maintained. In the present invention, in order to maintain the regeneration temperature and supply the required amount of heat of carbon dioxide gas release and sensible heat of the filler, heating by an external heating device 211 or heat of oxidation reaction by a burner 212a is used.
[0049]
Further, in order to increase the purity of the released carbon dioxide gas and reuse it, it is preferable to employ heating by an external heating device 211, and when the burner 212a in the reactor 212 is used, high purity is used. It is preferable to use oxygen gas as the oxidizing agent.
[0050]
Also, in Step 1, it is most preferable to employ a heating source using the burner 212a. The reason is that the heating device 211 itself is not required separately as in the heating method using the external heating device 211, and is economically excellent. In addition, the external heating device 211 is disadvantageous in that the device itself is exposed to a high temperature, so that a relatively high-grade member needs to be used as a structural member.
[0051]
Although not shown in FIG. 2, the carbon dioxide-containing gas discharged from the reactor outlet 217 can be pressurized and recycled.
[0052]
The end of Step 2 can be confirmed by monitoring the gas temperature at the reactor outlet 217 with a thermometer 215b and detecting the boundary between the regeneration temperature and the absorption temperature. Further, the time required for Step 2 can be changed by controlling the flow rate of the carbon dioxide-containing gas supplied (or circulated) to the reactor 212.
[0053]
In step 3, the carbon dioxide-containing gas remaining in the reactor 212 is discharged, and the mixed gas (raw material gas) of the carbon-containing fuel and steam described in step 1 is supplied to the reactor 212 via the line 223 and the switching valve 214c. It begins by feeding from the reactor inlet 219 below 212. However, immediately after the start of step 3, the packed bed 212b in the reactor 212 is maintained at the regeneration temperature, and the raw material gas undergoes the reforming reaction by the reforming catalyst, but the carbon dioxide generated by the reforming reaction is carbon dioxide. The packing layer 212b is not absorbed by the absorbing material, but causes only the reforming reaction, and the carbon dioxide passes through.
[0054]
On the other hand, when the reforming reaction occurs, the temperature of the packed layer 212b gradually decreases due to the endothermic reaction, and decreases to the absorption temperature at which carbon dioxide starts to be absorbed by the carbon dioxide absorbent. Therefore, the boundary temperature (for example, 700 ° C.) at which carbon dioxide is absorbed and released moves toward the flow direction of the raw material gas, and moves within the packed bed 212b with time. The reforming reaction and the carbon dioxide absorption reaction occur simultaneously on the upstream side of the boundary temperature moving surface, and only the reforming reaction occurs on the downstream side. The moving speed of the boundary temperature depends on the sensible heat stored in the filler (the reforming catalyst, the carbon dioxide absorbent, and in some cases, the heat storage material). The moving speed is slow if the heat storage amount is large, and the moving speed is high if the heat storage amount is small. Therefore, the time required for step 3 depends on the amount of the filler.
[0055]
In Step 3, heating by the burner 212a used in Steps 1 and 2 is not always necessary, and the reaction may be performed adiabatically. Step 3 is completed when the required absorption temperature level of the filling layer 212b is reached in the subsequent step 1. The temperature of the reformed fuel gas at the reactor outlet 217 is monitored by a thermometer 215c, and it can be determined whether or not the temperature has reached the temperature.
[0056]
In FIG. 2, in step 3, the source gas flows from bottom to top, but may flow from top to bottom. However, considering that the next step 1 is to flow from the top to the bottom, if the cooling in the step 3 is insufficient and the high-temperature zone remains on the upper part of the filling layer 212b, this step 1 Since the raw material gas is supplied to the high-temperature zone, and there is a possibility that carbon dioxide cannot be absorbed, it is preferable to flow the gas in a direction opposite to the flow direction of step 1.
[0057]
In FIG. 2, the flow direction of the gas in the reactor 212 in each step is described as flowing from top to bottom in steps 1 and 2, and from bottom to top in step 3, but the most desirable flow direction In the present invention, the flow direction can be arbitrarily selected.
[0058]
Further, it is preferable to discharge and purge the gas in the previous step remaining in the reactor 212 between each step. However, depending on the composition and properties of the remaining gas, the gas can be mixed with the reformed fuel. Although not shown in the figure, the gas may be separately treated by an exhaust gas treatment device (not shown), and may be effectively used as appropriate.
[0059]
As described above, in the embodiment described with reference to FIG. 2, steps 1 to 3 are sequentially and periodically repeated, so that the reformed fuel is continuously output, and the carbon dioxide gas absorbed and released is continuously output. Although it is impossible to take out, for example, it is possible to take out continuously by using a plurality of reactors.
[0060]
Using three reactors of the same shape and size, each is allocated to the steps 1, 2 and 3, and the time required to complete each step is filled with the carbon dioxide absorbing material so that all the times are the same. The required time can be adjusted by adjusting the amount, the supply (circulation) flow rate of the carbon dioxide-containing gas, and, in some cases, the filling amount of the heat storage material.
[0061]
The embodiment will be described with reference to FIG. In FIG. 1, a line indicated by a thick line indicates a line in use, and a line indicated by a thin line indicates a line which is not used.
[0062]
Here, three reactors 12, 13, and 14 are used. Each of the reactors 12, 13, and 14 is filled with a fuel reforming catalyst, a carbon dioxide absorbent, and, if necessary, a heat storage material. These reactors 12, 13, and 14 are operated by repeating the three steps sequentially and periodically. FIG. 4 shows a timing chart of an example of an operation method of the system of this embodiment. Here, the time required for each step shown in FIG. 3 is made equal, and the three reactors 12, 13, and 14 are sequentially and periodically operated while shifting the steps one by one.
[0063]
The carbon-containing fuel 1 is sent to the desulfurizer 11 through a line 31 in order to remove a sulfur content that significantly affects the catalytic activity of the fuel reforming catalyst and the absorption capacity of the carbon dioxide absorbent. As a filler to be filled in the desulfurizer 11, activated carbon or the like having a desulfurizing ability is sufficient, and a commercially available desulfurizing agent may be appropriately used. If the raw material does not require desulfurization, desulfurization can be omitted.
[0064]
The carbon-containing fuel from which the sulfur content has been removed passes through the line 32 and has a predetermined steam and carbon / steam (molar flow rate of steam / molar carbon flow rate in the carbon-containing fuel) ratio of preferably 1 to 5. A mixed gas (hereinafter, sometimes referred to as a raw material gas) mixed with steam is heated to a predetermined temperature, preferably 400 to 700 ° C. in the heat exchanger 15, passes through the line 33, and undergoes a cooling / fuel reforming process (step 3). )).
[0065]
[Cooling / fuel reforming process] (Step 3)
The reactor 13 in the cooling / fuel reforming step (step 3) has completed the absorbent regeneration / heat storage step (step 2), at which point the reactor 13 preferably has a temperature of 700 to 900 ° C. I have.
[0066]
The raw material gas is supplied to the reactor 13 through the line 33. This supply is preferably performed from the lower side of the reactor 13. After completion of the cooling / fuel reforming step (step 3), the process proceeds to the fuel reforming / carbon dioxide separation step (step 1). If the cooling of the packed bed 13b happens to be insufficient, the upper part of the packed bed 13b is When the next fuel reforming / carbon dioxide separation step (step 1) is started in a state where the high-temperature zone remains, the carbon dioxide absorption in the high-temperature zone does not occur, and the reforming reaction occurs. There is a possibility that carbon dioxide generated in the process will pass through.
[0067]
Therefore, in order to reliably absorb the carbon dioxide generated by the reforming reaction, it is preferable to supply the raw material gas from the lower side of the reactor 13 in which the raw material gas is surely cooled to the absorption temperature. The raw material gas supplied from the lower side of the reactor 13 in the cooling / fuel reforming step (step 3) through the line 33 is directed upward from the lower side of the reactor 13 while gradually causing a fuel reforming reaction. As a result, cooling takes place from the bottom side, and the said purpose is achieved. Preferably, the supply is from the lower side, but it is also possible to supply from the upper side.
[0068]
The raw material gas undergoes a fuel reforming reaction by the amount of heat stored in the carbon dioxide absorbing material in the reactor 13 and the heat storage material filled as necessary, and the raw material gas is partially converted to reformed fuel. In the cooling / fuel reforming step (step 3), the carbon dioxide absorbent that has released the carbon dioxide at the regeneration temperature is cooled using the reaction heat of the reforming reaction. In some cases, the sensible heat of the heat storage material is used as the reaction heat of the reforming reaction. In the cooling / fuel reforming step (step 3), the reforming reaction is performed under adiabatic conditions, and the gas temperature at the outlet of the reactor 13 changes with time depending on the sensible heat of these available fillers. .
[0069]
Therefore, it is sufficient that carbon dioxide has reached the absorption temperature at which carbon dioxide can be absorbed by the carbon dioxide absorbent at the end of the cooling / fuel reforming step (step 3), and the end time of this step can be extended by adding a heat storage material. Alternatively, this step can be completed in the shortest time when the heat storage material is not added. Whether or not the heat storage material is added can be appropriately determined and selected based on the cycle time (the time required for one cycle) of each process (step 1 to step 3) and the flow rate of the raw material gas.
[0070]
[Fuel reforming / carbon dioxide separation process] (Step 1)
A raw material gas containing a reformed fuel in which part of the carbon-containing fuel 1 has been converted to hydrogen (hereinafter sometimes referred to as a partially reformed raw material gas) passes through a line 34 and undergoes fuel reforming and carbon dioxide separation. It is supplied to the reactor 12 in the process (step 1). In the upper part of the reactor 12 (upstream from the fuel reforming catalyst and the carbon dioxide absorbent) in the fuel reforming / carbon dioxide separation step (step 1), a part of the partially reformed raw material gas supplied from the line 34 And / or the carbon-containing fuel 1 supplied from the line 52 is supplied to the fuel reforming catalyst after being oxidized by the air 3 supplied from the line 51.
[0071]
In the air 3 supplied from the line 51, the reaction heat generated by the oxidation is the heat absorption of the fuel reforming reaction at the desired fuel reforming reaction temperature and the heat generation when the carbon dioxide is absorbed by the carbon dioxide absorbent. Only the amount corresponding to is supplied. Such a configuration is preferable because the carbon dioxide absorbent can be constantly brought to the absorption temperature and the fuel reforming reaction can be constantly and stably performed under the condition.
[0072]
When such an oxidizing means is not provided, the sensible heat of the filler, the heat generated by the absorption reaction of carbon dioxide into the carbon dioxide absorbent, and the heat absorption by the reforming reaction are balanced, and the inside of the reactor 12 The average temperature of the packing 12b tends to decrease with time as a whole, and the fuel reforming reaction cannot be performed constantly and stably. However, the temperature at the outlet of the reactor 12 is If the temperature is higher than a required temperature (for example, 400 ° C.), reforming is possible. It is only disadvantageous in that the performance as a supply device is inferior to the above-described embodiment, for example, the concentration of unconverted carbon-containing fuel in the generated reformed fuel increases and the hydrogen concentration decreases.
[0073]
In the oxidation in the fuel reforming / carbon dioxide separation step (step 1), air or oxygen-enriched air can be used in addition to air as an oxidizing agent. Oxygen and oxygen enriched air 4 can be supplied from line 53.
[0074]
As the oxidizing means, for example, means for blowing an oxidizing agent into the carbon-containing fuel 1 and / or the reformed fuel to oxidize or partially oxidize a part of the reformed fuel and / or the carbon-containing fuel 1 is used. Can be. For example, a burner 12a may be provided in the upper part of the reactor 12, and partial oxidation or oxidation may be performed here. Further, a part of the reformed fuel and / or the carbon-containing fuel 1 may be oxidized or partially oxidized outside the reactor 12 to utilize the heat of the oxidation reaction. Alternatively, a partial oxidation means can be provided.
[0075]
Here, the partial oxidation means that only a part of the unreacted carbon-containing fuel in the carbon-containing fuel 1 and / or the reformed fuel is oxidized and burned, and carbon monoxide and hydrogen are obtained as main reaction products. (In a sense, incomplete combustion), the above oxidation refers to a general oxidation reaction such as carbon dioxide, water, hydrogen, and carbon monoxide as a product, and is distinguished. By partial oxidation, hydrogen is generated in the product, the product hydrogen concentration increases, and the generated carbon monoxide is further reacted with steam by the reforming catalyst (causing a shift reaction described later), and oxidized to carbon dioxide. In this step, it is absorbed and separated by the carbon dioxide absorbent.
[0076]
In the reactor 12, a fuel reforming reaction preferably occurs at a temperature of 400 ° C. or more and less than 700 ° C., and the supplied partially reformed raw material gas is converted into reformed fuel, and at the same time, carbon dioxide is absorbed. Absorbed by the material. More preferably, the reforming temperature is from 500 to 600C. The temperature is preferably 400 ° C. or higher from the viewpoint of the degree of reaction progress of the fuel reforming reaction and the obtained hydrogen concentration. At 700 ° C. or higher, the reaction amount is large for the temperature increase from the viewpoint of the reforming reaction. It does not increase and is disadvantageous in terms of economy. Further, the carbon dioxide absorption rate and the carbon dioxide emission rate tend to be substantially balanced, which is disadvantageous in that substantial absorption of carbon dioxide hardly occurs.
[0077]
When absorption of carbon dioxide occurs, heat of absorption corresponding to the amount of absorption is generated, and this heat of absorption is also used for the fuel reforming reaction. Furthermore, the equilibrium reaction shown below shifts due to the absorption of carbon dioxide by the carbon dioxide absorbent, and the reaction further proceeds, thereby promoting the production of hydrogen. The fuel reforming reaction is a simultaneous reaction in which the following reaction formula 1 and reaction formula 2 occur simultaneously. The reaction formula and the equilibrium formula are as follows. In the reaction formula, the carbon-containing fuel 1 is represented by methane.
[0078]
Steam reforming reaction formula: CH ₄ + H ₂ O⇔CO + 3H ₂ .. (Reaction formula 1)
Shift reaction Reaction formula: CO + H ₂ O⇔CO ₂ + H ₂ ... (Reaction formula 2)
Steam reforming reaction equilibrium equation:
K _pl = (P (H ₂ ) ³ × P (CO)) / (P (CH) ₄ ) × P (H ₂ O))
P (H ₂ ): Partial pressure of hydrogen gas. P (CO): partial pressure of carbon monoxide gas.
P (CH ₄ ): Partial pressure of methane gas. P (H ₂ O): partial pressure of water vapor.
Shift reaction equilibrium equation:
K _p2 = (P (H ₂ ) × P (CO ₂ )) / (P (CO) × P (H ₂ O))
P (H ₂ ): Partial pressure of hydrogen gas. P (CO ₂ ): Partial pressure of carbon dioxide gas.
P (CO): partial pressure of carbon monoxide gas. P (H ₂ O): partial pressure of water vapor.
[0079]
As the fuel reforming catalyst, a general-purpose nickel-based catalyst is preferable because the steam reforming reaction and the shift reaction are simultaneously performed, and a mixed catalyst obtained by appropriately mixing a catalyst suitable for each of the steam reforming reaction and the shift reaction is preferable. Good.
[0080]
As the carbon dioxide absorbent, a compound that reacts with carbon dioxide at a temperature at which the fuel reforming reaction proceeds to generate a carbonate is preferable, but a lithium-based compound capable of reversibly absorbing and releasing carbon dioxide is economical. Yes and preferred. Above all, it is more preferable to use a lithium composite oxide typified by lithium zirconate, lithium ferrite, and lithium silicate which generate lithium carbonate by reacting with carbon dioxide.
[0081]
The reason is that the carbon dioxide absorbent, which reacts with carbon dioxide to produce lithium carbonate, can extract carbon dioxide at a lower temperature than sodium carbonate, potassium carbonate, and calcium carbonate because the decomposition temperature of lithium carbonate is low. Because you can. Lithium zirconate is Li ₂ ZrO ₂ , Li ₄ ZrO ₄ Wherein the lithium ferrite is LiFeO 2 ₂ Is represented by the following chemical formula: In addition, in lithium silicate, lithium metasilicate (Li ₂ SiO ₃ ) And lithium orthosilicate (Li ₄ SiO ₄ ) Is known, and a reaction of the following formula in which lithium orthosilicate absorbs carbon dioxide can be particularly preferably used.
Li ₄ SiO ₄ + CO ₂ = Li ₂ SiO ₃ + Li ₂ CO ₃ ... (Reaction formula 3)
Further, an alkali metal carbonate and / or an alkaline earth metal carbonate such as sodium carbonate, potassium carbonate and calcium carbonate are appropriately added to a compound such as a lithium composite oxide which reacts with carbon dioxide to generate a carbonate, They can be used together. In this case, the carbon dioxide absorption / release speed of the carbon dioxide absorbent depends on the temperature and the type and concentration of the added carbonate, and the absorption / desorption reaction can be promoted by adding the carbonate.
[0082]
The hydrogen-rich gas, ie, reformed fuel, is generated from the lower part of the reactor 12 in the fuel reforming / carbon dioxide separation step (step 1), preferably at a temperature of 400 ° C. or more and less than 700 ° C. The produced reformed fuel passes through a line 35, is cooled by heat exchange between the mixed gas of the carbon-containing fuel 1 and the steam 2 in the heat exchanger 15, and is sent to a cooler 16 through a line 36, where it is further cooled. Then, after the water in the reformed fuel is separated and removed to the line 37, the reformed fuel is taken out from the line 38 as the product, the reformed fuel. In FIG. 1, a heat exchanger integrated with a separator that separates condensed water is used as the cooler 16, but there is no particular limitation on the type, and a type that matches the purpose may be selected.
[0083]
The form of heat recovery in the cooler 16 is not particularly limited, and heat recovery according to the purpose is possible. In particular, uncondensed water is contained in the reformed fuel, and it is conceivable to effectively use the heat of condensation of the uncondensed water. Various recovery methods are conceivable, for example, a heat source for generating steam 2 shown in FIG. 1, a heat source for preheating the carbon-containing fuel 1, a heat source for preheating the oxidant 4, and the like. good.
[0084]
[Absorbent regeneration and heat storage process] (Step 2)
On the other hand, when the fuel reforming / carbon dioxide separation step (Step 1) is completed, the process proceeds to the absorbent regeneration / heat storage step (Step 2). In the absorbent regeneration / heat storage step (step 2), the carbon dioxide-containing fuel, the reformed fuel, or other fuel is used as a heat source, preferably at a regeneration temperature of 700 to 900 ° C. to regenerate the carbon dioxide absorbent, that is, from the carbon dioxide absorbent. Emission of carbon dioxide takes place in reactor 14. The regeneration temperature is more preferably from 800 ° C to 850 ° C. If the regeneration temperature is lower than 700 ° C., the absorption rate and the release rate of carbon dioxide tend to be substantially balanced, which is disadvantageous in that substantial release is difficult to occur. This is disadvantageous in terms of deterioration of the apparatus such as the reactor 14 and the filler such as the carbon dioxide absorbent.
[0085]
In this step, the carbon dioxide absorbent is heated to the regeneration temperature by the heating means. Specifically, the fuel is oxidized by an oxidizing agent by an oxidizing means such as a burner 14a provided at an upper part in the reactor 14, and the produced gas is brought into contact with the carbon dioxide absorbent to regenerate the carbon dioxide absorbent. Heat can be stored. The fuel is not limited to the carbon-containing fuel 1, but a reformed fuel may be used, and other fuels may be used. In short, any fuel that can be used as a heat source in the regeneration of the carbon dioxide absorbent can be used here.
[0086]
Air can be used as the oxidizing agent, but by using oxygen or oxygen-enriched air and performing complete combustion (oxidation), carbon dioxide and water are obtained as oxidation products. Thus, a carbon dioxide-containing gas having a high carbon dioxide concentration and a low impurity concentration other than water can be obtained. Moisture in the carbon dioxide-containing gas can be easily separated and removed from the main component carbon dioxide only by cooling as described later, and further increase the carbon dioxide concentration in the carbon dioxide-containing gas after separation and removal. Can be. In addition, by using high-purity oxygen as the oxidizing agent, a carbon dioxide-containing gas having a much higher carbon dioxide concentration can be obtained.
[0087]
The oxidizing means such as the burner 14a used as the heating means and the oxidizing means such as the burner 12a used in the fuel reforming / carbon dioxide separation step (step 1) can be used together, which is more economical.
[0088]
In the reactor 14 in the absorbent regeneration / heat storage step (step 2), the fuel as the heat source passes through the line 41, the oxidant 4 passes through the line 42, and the fuel and the oxidant 4 are mixed. Supplied. The fuel is oxidized in the reactor 14 by the oxidant, and the reactor 14 is preferably heated to a temperature of 700 to 900 ° C. to regenerate the carbon dioxide absorbent. The fuel serving as a heat source is supplied in such an amount as to maintain the temperature required for the regeneration and heat storage of the carbon dioxide absorbent. The product gas (combustion gas) containing carbon dioxide released from the carbon dioxide absorbent is discharged from the lower side of the reactor 14, passes through the line 43, passes through the heat exchanger 17, where heat is recovered, and further cooled. Is cooled. The cooled gas containing carbon dioxide passes through a line 44 and is branched into a carbon dioxide-containing gas as a by-product and a recycled gas. Then, the carbon dioxide-containing gas is cooled by the cooler 18 through the line 45 and supplied to the greenhouse through the line 46. The cooling water used for cooling the carbon dioxide-containing gas in the cooler 18 becomes hot water by being heated by the carbon dioxide-containing gas in the cooler 18, and is supplied to the greenhouse through the line 60.
[0089]
The excess carbon dioxide-containing gas with respect to the supply to the greenhouse is returned to the absorbent regeneration / heat storage step (step 2) through the line 47, and is used as a recycle gas. It is supplied to the upper part of the vessel 14. That is, the pressure is increased to a pressure required for circulation by a pressure increasing means, here a blower 19, through a line 47, sent to the heat exchanger 17 through a line 48, and mixed with a high-temperature carbon dioxide-containing gas discharged from an outlet of the reactor 14. After the heat exchange, the temperature is raised to a predetermined temperature through a line 49, and then supplied to the upper side of the reactor 14, and used as a recycle gas in the absorbent regeneration / heat storage process (step 2).
[0090]
In the regeneration of the carbon dioxide absorbent, if the temperature of the packed bed 14b rises to the regeneration temperature, the reaction proceeds to the left according to the above-mentioned reaction formula 3 to release the absorbed carbon dioxide. In order to enhance the speed of heat transfer in the packed bed 14b, the same substance as the gas absorbed by the carbon dioxide absorbent is circulated, and the convection heat transfer is used in combination to improve the heat transfer speed and, consequently, the regeneration. Therefore, it is preferable to recycle the carbon dioxide since the required time can be shortened. The amount to be recycled may be determined so that the temperature after heating by the oxidizing means is 900 ° C. or less which does not adversely affect the carbon dioxide absorbent.
[0091]
In FIG. 1, the raw material introducing means is formed by, for example, a line 33 from the carbon-containing fuel 1 and the steam 2 to the reactor 13 and the desulfurizer 11 or the like, or the line 34 is also a raw material introducing means. The heating means is formed by providing the burners 12a, 13a, 14a upstream of the packed layers 12b, 13b, 14b of the reactors 12, 13, 14 filled with a carbon dioxide absorbent or the like.
[0092]
The switching means for switching between these uses is not shown, but can be formed by a valve appropriately provided on the line. If this valve is an automatic valve and a computer or the like for controlling the automatic valve is provided, the switching can be performed automatically. Switching timing control means for switching the timing of these switching means by shifting the timing can be formed by a computer or the like which controls the automatic valves by using these valves as automatic valves.
[0093]
FIG. 4 shows a temporal change of the operation timing corresponding to the configuration shown in FIG. 1. Gases generated in the respective reactors 12, 13, and 14 which are generated at the time of switching are appropriately purged as necessary, and the reaction is performed. It can be discharged outside the vessel, or can be mixed into the reformed fuel of the product or the carbon dioxide-containing gas supplied to the greenhouse. However, in this case, although the purity of the product is deteriorated, it may be effectively used as appropriate.
[0094]
As described above, the embodiment of the present invention has been described with reference to FIGS. 1 and 2. The present invention is shown in FIG. 2 and a supply device including three reactors 12, 13, and 14. The number of reactors is not limited to a single reactor 212, but may be appropriately determined according to the purpose.
[0095]
In the embodiment shown in FIG. 1, three independent reactors 12, 13, and 14 are used, and the reformed fuel can be continuously obtained by periodically and repeatedly operating. However, a partition wall is provided in one reactor. For example, it is also possible to divide the three steps, and the number of physical steps of the reactor is not limited.
[0096]
Next, the operation of the supply device according to the embodiment of the present invention configured as described above will be described.
[0097]
A city gas containing methane as a main component was used as the carbon-containing fuel 1, and a reforming fuel was obtained through the line 38 and a carbon dioxide-containing gas was obtained through the line 45 by the supply device having the configuration shown in FIG. . The composition of the city gas, the gas composition at each part, the temperature, etc. are as shown in FIG. 5, and the carbon dioxide contained in the carbon dioxide-containing gas at this time was 99.5 mol%.
[0098]
The carbon dioxide-containing gas containing such high-purity carbon dioxide is supplied to the greenhouse after being cooled by the cooler 18. On the other hand, the cooling water used for cooling the carbon dioxide-containing gas in the cooler 18 is heated by the carbon dioxide-containing gas in the cooler 18 and becomes hot water before being supplied to the greenhouse. Thereby, both carbon dioxide and hot water are supplied to the greenhouse.
[0099]
The supply device according to the embodiment of the present invention can supply both carbon dioxide and hot water required for plant cultivation in the greenhouse 62 by the above-described operation, as shown in FIG. . As a result, not only can the cost of heating the greenhouse 62 be reduced, but also environmentally friendly agricultural techniques can be introduced.
[0100]
Further, the supply device according to the embodiment of the present invention can supply a carbon dioxide-containing gas having an extremely high carbon dioxide content, as described above. The carbon dioxide-containing gas generated by this apparatus is different from that generated by a combustion gas supply system such as a carbon dioxide gas generator, and contains almost no components other than carbon dioxide. By performing plant cultivation using such a high-purity carbon dioxide-containing gas, plant growth can be promoted several times.
[0101]
Further, the supply device according to the embodiment of the present invention can supply hot water. Thereby, not only can water required for photosynthesis of plants be supplied at an appropriate temperature, but also the inside of the greenhouse 62 can be maintained at an appropriate temperature.
[0102]
Furthermore, in the supply device according to the embodiment of the present invention, it is possible to generate energy required for carbon dioxide emission by using hydrogen, which is a clean energy source obtained by a fuel reforming reaction. This makes it possible to operate efficiently with low energy consumption.
[0103]
In recent years, reduction of carbon dioxide emission has been regarded as important as a global warming countermeasure, and various technologies such as a carbon dioxide capture technology, a fixation technology, and a storage technology have been developed. However, using any of these technologies does not mean that carbon dioxide is reduced from the earth. The supply facility according to the embodiment of the present invention supplies carbon dioxide to plants and promotes a natural purification action of releasing oxygen, thereby helping to reduce carbon dioxide emissions.
[0104]
Although the preferred embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to such configurations. Within the scope of the invented technical concept of the claims, those skilled in the art will be able to conceive various changes and modifications, and those changes and modifications will be described in the technical scope of the present invention. It is understood that it belongs to.
[0105]
For example, by using a reformed fuel to generate light in a fuel cell or the like and supplying the light to the greenhouse 62, the supply device according to the embodiment of the present invention can supply carbon dioxide, hot water, light, etc. It is also possible to supply all the elements necessary for plant cultivation to the greenhouse. Alternatively, by increasing the size of the supply device according to the embodiment of the present invention, it is possible to supply carbon dioxide and hot water to a plurality of greenhouses provided throughout the area at once. It is.
[0106]
【The invention's effect】
As described above, according to the present invention, it is possible to realize a greenhouse carbon dioxide and hot water supply device that can efficiently supply both carbon dioxide and hot water to a greenhouse.
[Brief description of the drawings]
FIG. 1 is a process flow diagram illustrating a configuration example of a supply device according to an embodiment of the present invention.
FIG. 2 is a system configuration diagram showing a detailed configuration example of a reactor.
FIG. 3 is a typical timing chart showing an operation method of the supply device according to the embodiment of the present invention.
FIG. 4 is a timing chart showing a modification of the operation method of the supply device according to the embodiment of the present invention.
FIG. 5 is a diagram showing the components of city gas used in the supply device according to the embodiment of the present invention, the gas composition at each part, the temperature, and the like.
FIG. 6 is a conceptual diagram for explaining the operation of the supply device according to the embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Carbon containing fuel, 2 ... Steam, 3 ... Air, 4 ... Oxidizing agent, 11 ... Desulfurizer, 12, 13, 14, 212 ... Reactor, 12a, 13a, 14a, 212a ... Burner, 12b, 13b, 14b , 212b ... packed bed, 15, 17, 216 ... heat exchanger, 16, 18, 20 ... cooler, 19 ... blower, 31-38, 41-49, 51, 52, 53, 60, 221, 222, 223 ... line, 62 ... greenhouse, 211 ... heating device, 213, 214 ... switching valve, 215 ... thermometer, 217 ... reactor outlet, 218, 219 ... reactor inlet

Claims (9)

A reformer that is rich in hydrogen from a carbon-containing fuel and steam, and a supply device that obtains carbon dioxide and hot water and supplies the carbon dioxide and hot water to a greenhouse,
A fuel reforming catalyst for accelerating a fuel reforming reaction for producing carbon dioxide and hydrogen by reacting the carbon-containing fuel and the water vapor, and a carbon dioxide absorbent capable of reversibly absorbing and releasing the produced carbon dioxide And a reactor filled with
Raw material introduction means for introducing the carbon-containing fuel and the steam into the reactor,
At least one of a part of the reformed fuel obtained by the fuel reforming reaction and the carbon-containing fuel is oxidized with an oxidizing agent to obtain a product gas, and the product gas is used to regenerate the carbon dioxide absorbent at a regeneration temperature. Heating means for heating up to
Hot water supply means for supplying the cooling water heated by the carbon dioxide by cooling the carbon dioxide obtained by the fuel reforming reaction with the cooling water to the greenhouse as hot water,
A carbon dioxide supply device for a greenhouse, comprising: a carbon dioxide supply device for supplying the carbon dioxide cooled by the hot water supply device to the greenhouse. The carbon dioxide and hot water supply device for a greenhouse according to claim 1, wherein a heat storage material that stores heat energy of the generated gas is filled in the reactor. The carbon dioxide and hot water for a greenhouse according to claim 1 or 2, wherein absorption heat generated when the carbon dioxide absorbent absorbs carbon dioxide in the reactor is used as reaction heat of the fuel reforming reaction. Feeder. 4. The fuel reforming reaction according to claim 1, wherein at least one of the reformed fuel and the carbon-containing fuel is oxidized by an oxidizing agent, and reaction heat of the oxidation reaction is used as reaction heat of the fuel reforming reaction. The supply device of carbon dioxide and hot water for a greenhouse according to claim 1. The greenhouse according to any one of claims 1 to 4, further comprising a recycle unit configured to recycle carbon dioxide released from the carbon dioxide absorbent into a reactor having the carbon dioxide absorbent that has released the carbon dioxide. For hot water and carbon dioxide. The carbon dioxide and hot water supply device for a greenhouse according to claim 5, wherein the heating means heats the carbon dioxide absorbent with a mixed gas of the generated gas and the recycled carbon dioxide. The greenhouse carbon dioxide and hot water supply device according to claim 5, wherein the heating unit heats the carbon dioxide absorbent by indirectly heating the recycling unit. The carbon dioxide absorbent is a compound that reacts with carbon dioxide to form a carbonate, and at least one carbonate selected from the group consisting of an alkali metal carbonate and an alkaline earth metal carbonate. The supply device for carbon dioxide and hot water for a greenhouse according to any one of claims 1 to 7, wherein the device is any one of the added mixture. 9. The compound according to claim 1, wherein the compound that reacts with carbon dioxide to form a carbonate is at least one lithium composite oxide selected from the group consisting of lithium zirconate, lithium ferrite and lithium silicate. A carbon dioxide and hot water supply device for a greenhouse according to claim 1.

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