JP7206686B2 - Fuel gas adsorption cartridge, fuel gas adsorption device using the same, and method for judging replacement timing of fuel gas adsorption cartridge - Google Patents

Description

The present invention relates to a fuel gas adsorption cartridge capable of determining replacement timing and a fuel gas adsorption apparatus using the same. The present invention also relates to a method for judging the replacement timing of a fuel gas adsorption cartridge, which enables replacement before the fuel gas adsorption capacity of the fuel gas adsorption cartridge breaks through.

Conventionally, when replacing gas meters for city gas or replacing propane gas cylinders, fuel gas remains in the pipes. It is not preferable because it spreads. Conversely, when purging the fuel gas pipe, it is necessary to replace the inside of the pipe with the fuel gas, and the mixed gas of the fuel gas and the air inside the pipe is discharged until the calorie reaches a predetermined value. There is a need to. In such a case, methane gas, which is a component of city gas, is lighter than air, while propane gas is heavier than air, so fuel gas leaks in high-rise condominiums should be considered not only on the working floor but also on the floors above and below. It is necessary to consider the surroundings of the neighborhood on the ground floor. Therefore, conventionally, leakage of fuel gas is prevented by connecting a decompressed gas adsorption container filled with a gas adsorbent and causing the gas adsorption container to adsorb fuel gas.

However, in this method of adsorbing fuel gas in the decompression container, not only fuel gas but also mixed gas components and air are adsorbed together, and when the pressure inside the container becomes normal pressure, adsorption becomes impossible, so a sufficient amount of fuel gas is required. In order to adsorb , it is necessary not only to increase the size of the container, but also to make it pressure resistant as a decompression container. Workability such as carrying is not good due to excessive weight.

Therefore, recently, a transient type fuel gas adsorption cartridge is also being developed, which selectively adsorbs target fuel gas components when the fuel gas passes through the gas adsorbent, since it is possible to reduce the size of the cartridge. In this transient fuel gas adsorption method using a gas adsorbent, in order to prevent fuel gas leakage, the timing of passage of the gas adsorbent is grasped and the fuel gas purging process is stopped in advance. It is necessary to replace the fuel gas adsorption container used in the purging process in advance in order to prevent fuel gas from leaking into the atmosphere and improve safety.

In the case of such a transient type gas adsorption cartridge, by grasping the gas adsorption amount in advance in order to predict the time when the gas adsorption material will break through, it is possible to approximate gas processing end time is predicted, and gas leakage is detected using a sensor that measures the concentration of the fuel gas to be adsorbed.

However, in the method of estimating the gas processing end time from the absolute amount of the cumulative flow rate of ventilation and the gas concentration, the processing end time must be set with a certain margin in order to completely prevent fuel gas leakage. There is a problem that the gas adsorbent in the gas adsorption cartridge cannot be used effectively. In addition, in the method of detecting gas leakage using a sensor that measures the concentration of the fuel gas to be adsorbed, not only can it be detected only after the fuel gas has leaked, but even if the fuel gas is detected, There is also the problem that it may leak temporarily due to fluctuations in the concentration of the fuel gas on the upstream side, and it is not always possible to determine whether the gas adsorbent has passed through.

On the other hand, there is also a method of investigating and analyzing how much gas adsorption has progressed in the gas adsorbent. In this method, the gas adsorbent breaks through the fuel gas adsorption cartridge from the upstream side with respect to the direction of gas flow. In this method, samples are taken out from each of the first stage, the middle stage, and the second stage, and the progress of deterioration of the fuel gas adsorption capacity of the sample is analyzed and confirmed before it passes through. However, with this method, not only is maintenance complicated, it takes time to obtain analysis results, and it is not realistic because only approximate results can be obtained unless stopping and analysis are repeated many times. there is a point

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fuel gas adsorption cartridge capable of judging when to replace it, and a fuel gas adsorption device using the same. Another object of the present invention is to provide a method for judging the replacement timing of a fuel gas adsorption cartridge, which enables replacement before the fuel gas adsorption capacity of the fuel gas adsorption cartridge breaks through.

In order to solve the above-mentioned problems, the first aspect of the present invention is a fuel gas adsorption cartridge comprising a fuel gas adsorption container having an inlet and an outlet filled with a fine-grained porous gas adsorbent, wherein the fine-grained porous Provided is a fuel gas adsorption cartridge in which at least a part of a raw gas adsorbent adsorbs a component with lower adsorptivity than a fuel gas to be adsorbed (Invention 1).

According to this invention (invention 1), by using a fine-grained porous gas adsorbent that adsorbs a component with lower adsorptivity than the fuel gas to be adsorbed, the fuel gas is adsorbed from the inlet of the fuel gas adsorption cartridge. When the fuel gas is circulated, the fine-grained porous gas adsorbent that adsorbs components with lower adsorptivity than the fuel gas adsorbs the fuel gas, while the components with lower adsorptivity than the adsorbed fuel gas are discharged from the outlet. Since it flows out, by detecting this with a sensor and monitoring the behavior (increase or decrease) of the concentration of the low-adsorptive component, the breakthrough timing of the fuel gas adsorption cartridge can be predicted in advance.

Secondly, in the present invention, a fuel gas adsorption container having an inlet and an outlet is filled with a fine-grained porous gas adsorbent, and at least a part of the fine-grained porous gas adsorbent is an adsorption target. A fuel gas adsorption device, comprising: a fuel gas adsorption cartridge that adsorbs a component with lower adsorptivity than fuel gas; (Invention 2).

According to this invention (invention 2), the fuel gas to be adsorbed is introduced from the inlet of the fuel gas adsorption cartridge filled with the fine-grained porous gas adsorbent that adsorbs a component with lower adsorptivity than the fuel gas to be adsorbed. When the gas is circulated, the fine-grained porous gas adsorbent that adsorbs the components with lower adsorptivity than the fuel gas adsorbs the fuel gas, while the components with lower adsorptivity than the adsorbed fuel gas flow out from the outlet. Therefore, by detecting this with a sensor for low-adsorptive components provided on the outlet side of the fuel gas adsorption container and monitoring the behavior (increase or decrease) of the concentration of the low-adsorptive components, the fuel gas adsorption cartridge can be predicted in advance.

In the above invention (invention 2), the fuel gas to be adsorbed is preferably methane gas, propane gas, butane gas, or a mixed gas containing these gases as main components (invention 3).

According to this invention (Invention 3), it is possible to suitably cope with the adsorption of methane gas, propane gas, butane gas, or mixed gas containing these gases as main components, which are generally distributed as fuel gases.

In the above inventions (inventions 2 and 3), the fine-grained porous gas adsorbent is preferably selected from carbonaceous porous materials, zeolite, silica gel and porous alumina (invention 4).

According to this invention (Invention 4), these fine-grained porous gas adsorbents can adsorb fuel gas, and adsorb nitrogen, oxygen, water, alcohols, etc. with a weaker adsorption force than fuel gas. If the fuel gas is adsorbed in a state where it has been adsorbed in advance, these components will be released. By detecting this, it is possible to detect the breakthrough timing of the fuel gas adsorption cartridge in advance. .

In the above inventions (inventions 2 to 4), the fine-grained porous gas adsorbent that adsorbs the low adsorptive component is arranged downstream of the fuel gas adsorption container with respect to the flow direction of the fuel gas. (Invention 5).

According to this invention (Invention 5), when the fine-grained porous gas adsorbent adsorbing the low adsorptive component adsorbs the fuel gas, the low adsorptive component is released instead. The fine-grained porous gas adsorbent breaks through from the upstream side of the fuel gas adsorption container in the flow direction of the fuel gas, and then gradually progresses toward the downstream side. When the concentration of the low adsorptive components in the exhaust gas rises and begins to decline, it means that the fuel gas adsorption cartridge is about to break through. It is possible to determine when to replace the battery.

In the above invention (invention 5), the fine-grained porous gas-adsorbing material that adsorbs the low-adsorptive component is 2 to 50% by volume of the total amount of the fine-grained porous gas-adsorbing material gas. is preferred (Invention 6).

According to this invention (Invention 6), the fine-grained porous gas adsorbent that adsorbs a component with low adsorptivity is arranged downstream of the fuel gas adsorption container with respect to the flow direction of the fuel gas. As a result, it is possible to secure an appropriate time from the release of the low-adsorptive component to the breakthrough of the fuel gas adsorption cartridge, thereby preventing the fuel gas from leaking and detecting the low-adsorptive component too early. Therefore, it is possible to easily ascertain the timing of breakthrough.

Furthermore, thirdly, the present invention comprises a fuel gas adsorption container having an inlet and an outlet, filled with a fine-grained porous gas adsorbent, and at least part of the fine-grained porous gas adsorbent becomes an adsorption target. The gas to be adsorbed is circulated from the inlet side of the fuel gas adsorption container of the fuel gas adsorption cartridge, which adsorbs a component lower in adsorptivity than the fuel gas, and the gas to be adsorbed is provided at the outlet side of the fuel gas adsorption cartridge. There is provided a fuel gas adsorption cartridge replacement timing determination method for predicting the gas adsorption capacity of the fuel gas adsorption cartridge by measuring the low adsorptive component with the sensor for the low adsorptive component (Invention 7).

According to this invention (invention 7), the fuel gas to be adsorbed is introduced from the inlet of the fuel gas adsorption cartridge filled with the fine-grained porous gas adsorbent that adsorbs a component with lower adsorptivity than the fuel gas to be adsorbed. When the gas is circulated, the fine-grained porous gas adsorbent that adsorbs the components with lower adsorptivity than the fuel gas adsorbs the fuel gas, while the components with lower adsorptivity than the adsorbed fuel gas flow out from the outlet. Therefore, by detecting this with a sensor for low-adsorptive components provided on the outlet side of the fuel gas adsorption container and monitoring the behavior (increase or decrease) of the concentration of the low-adsorptive components, the fuel gas adsorption cartridge Since it is possible to predict in advance the timing of the passage of the fuel gas, it is possible to determine the replacement timing of the fuel gas adsorption cartridge.

In the fuel gas adsorption apparatus of the present invention, a fuel gas adsorption container is filled with a fine-grained porous gas adsorbent having at least a portion thereof adsorbed with a low-adsorptive component. Since it is provided with a low-adsorbent sensor, the fuel gas adsorption cartridge can be replaced by detecting the low-adsorbable component with the sensor and monitoring the increase or decrease in the concentration of the low-adsorbable component. By judging the timing, it is possible to prevent leakage of fuel gas.

FIG. 3 is a schematic diagram showing a filling state of a fuel gas adsorption cartridge of the fuel gas adsorption device according to one embodiment of the present invention; It is a schematic diagram showing a fuel gas adsorption device according to the embodiment. 4 is a graph showing the propane gas concentration at the inlet and outlet of the fuel gas adsorption apparatus of Examples 1 and 2, and the carbon dioxide concentration at the outlet. 4 is a graph showing the concentration of carbon dioxide at the outlet of the fuel gas adsorption device in FIG. 3;

The fuel gas adsorption device of this embodiment will be described in detail below.

The fuel gas adsorption device of the present embodiment includes a fuel gas adsorption cartridge and a fuel gas adsorption material provided on the outlet side of the fuel gas adsorption cartridge that is more adsorbent than the fuel gas to be adsorbed, which will be described later. It consists of a low component sensor. This fuel gas adsorption cartridge comprises a fine-grained porous gas adsorbent and a transient fuel gas adsorption container having an inlet and an outlet filled with the fine-grained porous gas adsorbent. Each component will be described below.

[Fuel gas]
In this embodiment, the fuel gas to be adsorbed is a hydrocarbon gas such as methane gas, propane gas, or butane gas, or a mixed gas containing these gases as main components. It can be suitably applied to those containing agents. Among these, propane gas and methane gas are preferred.

[Fuel gas adsorption cartridge]
(Fuel gas adsorption vessel)
In this embodiment, the fuel gas adsorption container filled with the fine-grained porous gas adsorbent is of the one-pass type, and has an inlet and an outlet with both ends of the column-shaped or rectangular-cylindrical container being open. It is possible to use a housing in which is formed, or a cylindrical or rectangular tubular container having an inlet portion and an outlet portion formed by a hollow discharge tube. A tube connected to a fuel gas source is connected to the inlet, and a discharge tube is connected to the outlet.

(Fine granular porous gas adsorbent)
In the present embodiment, the fine-grained porous gas adsorbent is not particularly limited as long as it is a porous material having gas adsorption ability, and inorganic porous materials and carbon-based porous materials can be preferably used.

Examples of inorganic porous materials include porous silica, metal porous structures, calcium silicate, magnesium silicate, magnesium aluminometasilicate, zeolite, porous alumina, titanium oxide, apatite, porous glass, magnesium oxide, and silicic acid. Aluminum or the like can be used. Further, fine granular activated carbon can be used as the carbon-based porous material.

These inorganic porous materials and carbonaceous porous materials may be used alone, or two or more of them may be used in combination. Among these, carbon-based porous materials, zeolite, silica gel, or porous alumina are preferred, and fine granular carbon-based porous materials are particularly preferred.

This fine-grained carbon-based porous material generally has selectivity of adsorbable molecules depending on pore size and polarity. Therefore, by adjusting the pore diameter and polarity, it can be made suitable for fuel gases to be adsorbed, such as methane gas, propane gas, and butane gas. Specifically, the fine particulate carbon-based adsorbent preferably has an average pore diameter of 20 Å or less. If the average pore diameter is larger than 20 Å, it becomes difficult to retain the adsorbed fuel gas. As for the lower limit of the average pore diameter, it is difficult to make the average pore diameter smaller than 4 Å. If the fine-grained carbon-based adsorbent is less than 0.3 mm, the pressure loss when the fuel gas is passed through becomes too large. is preferably

When the fine particulate carbon-based adsorbent adsorbs a polar fuel gas such as propane gas or butane gas, it is preferable that the surface functional groups are adjusted to impart polarity. Adjustment of the surface functional groups of the fine particulate carbonaceous adsorbent can be performed by activating the fine particulate carbonaceous adsorbent with carbon dioxide gas, nitrogen gas or argon gas. Specifically, the surface of the untreated (initial state) fine granular carbon-based adsorbent has carboxyl groups and phenolic hydroxyl groups, but by activating with carbon dioxide, all or part of them are —CH terminals can be In particular, by impregnating bromine on the surface of the fine granular carbon-based adsorbent to form a bromine-impregnated supported activated carbon, the selective adsorbability of fuel gas and the adsorbability of odorant can be improved, which is preferable.

This activated carbon impregnated with bromine is produced by, for example, heat-treating the activated carbon at 350 to 900° C. in the absence of oxygen to remove moisture and chlorides contained in the activated carbon, and adding about 1 to 15% by weight of bromine to the obtained activated carbon. It can be obtained by attaching.

The fine particulate carbonaceous adsorbent preferably has a surface area of 100 to 1000 m ² /g, preferably 200 to 800 m ² /g.

These specific surface area, pore volume and average pore diameter are values measured by, for example, "BELSORP-max" (trade name) manufactured by Microtrack Bell.

(Structure of fuel gas adsorption cartridge)
The fuel gas adsorption cartridge is obtained by filling a fuel gas adsorption container as described above with a fine particulate porous gas adsorbent.

Here, fine-grained porous gas adsorbents, particularly fine-grained carbon-based adsorbents, have different adsorptive properties depending on the target to be adsorbed. For example, taking typical adsorptive substances as an example, their adsorptive strengths are in the following order.
Propane gas > CO ₂ > methane gas > nitrogen > oxygen > water > methanol

Therefore, in the present embodiment, at least a part of the fine-grained porous gas adsorbent is made by adsorbing a component having a lower adsorptive property than the fuel gas to be adsorbed. Specifically, when the fuel gas to be adsorbed is propane gas, _CO2 is pre-adsorbed, and when the fuel gas to be adsorbed is methane gas, nitrogen or oxygen, or water or methanol is used. It is preferable to use one that has been adsorbed in advance.

Specifically, the fuel gas adsorption cartridge preferably has a filling structure as shown in FIG. In FIG. 1, a fuel gas adsorption cartridge 1 is provided with a gas inlet member 3 as an inlet at the top and a discharge pipe 4 as an outlet extending from the bottom. Spacer members 5A and 5B, through which the gas can flow and which does not permeate the fine-grained porous gas adsorbent, are installed at the upper and lower ends of the gas flow direction (from the gas inflow member 3 to the bottom of the discharge pipe 4). The fine-grained porous gas adsorbent 6 (which does not adsorb low-adsorbable components) is on the upstream side of the direction), and the downstream side adsorbs components with lower adsorptive properties than the fuel gas to be adsorbed. It has a transient structure in which fine-grained porous gas adsorbents 7 are arranged respectively. That is, in this embodiment, the lower end of the gas inflow member 3 communicates with the spacer member 5A, and the lower end of the discharge pipe 4 communicates with the spacer member 5B. The outer shell of the fuel gas adsorption container 2 can be made of metal such as stainless steel, and the exhaust pipe 4 and spacer members 5A and 5B can be made of resin such as polypropylene. Such a one-time type fuel gas adsorption cartridge 1 has a small volume of 5000 cc or less and is excellent in handleability compared to a decompression type container in which the inside of a container filled with a gas adsorbent is decompressed to suck and adsorb fuel gas. , has the characteristics of

The reason why such a structure is preferable is as follows. That is, when propane gas G (including mixed gas of propane gas G) as fuel gas is supplied from the gas inflow member 3 of the fuel gas adsorption container 2, the propane gas G flows through the entire periphery of the fuel gas adsorption container 2 in the spacer member 5A. It diffuses in the direction and flows into the fine-grained porous gas adsorbent 6, and the fine-grained porous gas adsorbents 6 and 7 adsorb propane and odor components in the propane gas G. Then, only the exhaust gas G1 that does not contain the propane gas G is exhausted from the spacer member 5B through the exhaust pipe 4. If such treatment is continued, the fine-grained porous gas adsorbents 6 and 7 will break through from the upstream side and gradually progress toward the downstream side. Then, when the fine-grained porous gas adsorbent 7 adsorbing the low-adsorptive component adsorbs the propane gas G, the previously adsorbed low-adsorptive component is released instead. By detecting low-adsorptive components in the exhaust gas G1 from the discharge pipe 4 and monitoring their behavior (concentration change), the breakthrough timing of the fuel gas adsorption cartridge 1 can be predicted in advance.

The fine-grained porous gas adsorbent 7 that adsorbs this low-adsorptive component is downstream of the fuel gas adsorption vessel 2 in the direction of gas flow, and has a length equal to or greater than the adsorption zone of the fine-grained porous gas adsorbent. It is preferable to set the volume to 5 times or less of the adsorption zone. If the fine-grained porous gas adsorbent 7 that adsorbs the low-adsorptive component is shorter than the adsorption band of the fine-grained porous gas-adsorbent, the fuel gas adsorption cartridge 1 will break after the low-adsorptive component is detected. The time until it passes is short, the stop of the distribution of propane gas G as fuel gas is not in time, and the propane gas G tends to leak, while the adsorption zone by the fine-grained porous gas adsorbent exceeds 5 times. As a result, components with low adsorption properties are released in a short period of time, and long-term monitoring is required to ascertain the timing of breakthrough, which is not preferable.

In general, the fine-grained porous gas adsorbent 7 that adsorbs components with low adsorptivity is placed on the downstream side of the fuel gas adsorption container 2 in the direction of gas flow. Based on 100% by volume of the solid gas adsorbent 6 and the fine granular porous gas adsorbent 7), the content is preferably 2 to 50% by volume, particularly 3 to 30% by volume. If the fine-grained porous gas adsorbent 7 adsorbing the low-adsorptive component is less than 2% by volume, the time from detection of the low-adsorptive component to breakthrough of the fuel gas adsorption cartridge 1 becomes short. , Propane gas G as a fuel gas cannot be stopped in time, and propane gas G tends to leak. It is not preferable because long-term monitoring is required to ascertain the timing of breakthrough.

[Sensor]
In this embodiment, a sensor capable of detecting a component with lower adsorptivity than the fuel gas to be adsorbed is used as the sensor. Specifically, when _CO2 is adsorbed, a carbon dioxide gas sensor is used, when nitrogen or oxygen is adsorbed, each sensor is used for nitrogen and oxygen, and when water or methanol is adsorbed, a humidity sensor is used. Alternatively, an alcohol meter may be used.

[Method for judging replacement timing of fuel gas adsorption cartridge]
Next, a method for judging the replacement timing of the fuel gas adsorption cartridge using the fuel gas adsorption device as described above will be described.

FIG. 2 shows a test apparatus for judging whether or not it is possible to determine the replacement timing of the fuel gas adsorption cartridge using the fuel gas adsorption apparatus according to one embodiment of the present invention. is a fuel gas adsorption cartridge 12 in which a fuel gas adsorption container 13 is filled with a fine-grained porous gas adsorbent, and a fuel gas supply pipe connected to an inlet portion 14 of the fuel gas adsorption container 13 of the fuel gas adsorption cartridge 12. 14A and a discharge pipe 15A connected to the outlet 15. As shown in FIG. The outlet 15 is a tubular member in this embodiment and extends to the bottom of the fuel gas adsorption vessel 13 . The discharge pipe 15A is provided with a calorimeter 16 and a CO ₂ sensor 17 capable of detecting a component (CO ₂ in this embodiment) that is less adsorbable than the fuel gas to be adsorbed. On the other hand, a gas cylinder 18 of propane gas G as a fuel gas is connected to the base end side of the fuel gas supply pipe 14A, and a flow meter 19 is provided. Reference numeral 20 denotes an opening/closing valve for starting/stopping the supply of propane gas G. FIG. In such a test apparatus, the fine-grained porous gas adsorbent filled in the fuel gas adsorption cartridge 12 has previously adsorbed CO ₂ on the downstream side of the fuel gas adsorption container 13 in the gas flow direction of the propane gas G. are placed.

In the test apparatus as described above, the opening/closing valve 20 is opened to supply the propane gas G from the gas cylinder 18 . At this time, the flow rate of the propane gas G is measured by the flow meter 19 . The propane gas G flows through the fuel gas supply pipe 14A into the fuel gas adsorption vessel 13 from the inlet 14, and passes through the fine-grained porous gas adsorbent in the fuel gas adsorption vessel 11 to form fine particles. The propane component and the odor component in the propane gas G are adsorbed by the porous gas adsorbent. Then, the heat quantity of the exhaust gas G1 discharged from the outlet portion 15 is measured by the calorimeter 16 and the CO ₂ concentration is measured by the CO ₂ sensor 17 .

As the propane gas G continues to flow, the fine-grained porous gas adsorbent breaks through from the inlet 14 side, and gradually progresses toward the downstream side with respect to the flow direction of the propane gas G. At this time, in the present embodiment, since the fine-grained porous gas adsorbent to which CO ₂ has been adsorbed in advance is arranged on the downstream side of the fuel gas adsorption container 13, the fine-grained porous gas to which the CO ₂ has been adsorbed When the breakthrough progresses to the area of the adsorbent and the propane gas G is adsorbed, CO ₂ which is a component with low adsorption is released instead. As a result, the CO ₂ concentration in the exhaust gas G ₁ detected by the CO ₂ sensor 17 increases. can be determined when it is possible to efficiently use the

Specifically, when the fine-grained porous gas adsorbent that has adsorbed CO ₂ adsorbs propane gas G, it releases CO ₂ instead.
This is due to a chemical reaction such as the following formula (1).
R-CO ₂ +C ₃ H ₈ →RC ₃ H ₈ +CO ₂ ↑ + heat of adsorption (1)
(wherein R is a gas adsorbent)

As a result, the concentration of CO ₂ in the exhaust gas G1 increases as the breakthrough of the fine-grained porous gas adsorbent layer that adsorbs CO ₂ progresses, then reaches a peak, and this state is maintained for a while. . Then, as the breakthrough of the fine-grained porous gas adsorbent layer that adsorbs CO ₂ progresses and the fuel gas adsorption capacity begins to decline, the CO ₂ concentration exhibits a downward behavior, and when it has completely dropped It can be considered that the fuel gas adsorption cartridge 12 has completely broken through. Therefore, from the volume of the fuel gas adsorption container 13, the volume of the fine granular porous gas adsorbent, the volume of the fine granular porous gas adsorbent to which CO ₂ has been adsorbed in advance, and the flow rate and concentration of the propane gas G, the increase → peak →By appropriately setting whether the fuel gas adsorption cartridge 12 should be replaced at any point in the descent, it is possible to reliably prevent the propane gas G from leaking and to efficiently use the fine-grained porous gas adsorbent. A possible replacement time can be determined.

Although the fuel gas adsorption device of the present embodiment has been described above, the present invention is not limited to the above embodiment, and various modifications are possible. For example, the fine-grained porous gas adsorbent 7 that adsorbs a component with low adsorption properties is preferably placed downstream of the fuel gas adsorption vessel 2, but it does not have to be the most downstream, and it may be placed in the middle of the downstream. may be placed. Furthermore, the fine-grained porous gas adsorbent 7 may be present in the fuel gas adsorption container 2, and the entire amount of the fine-grained porous gas adsorbent may be made to adsorb a low-adsorptive component, In some cases, a mixture of a fine-grained porous gas adsorbent 6 and a fine-grained porous gas adsorbent 7 that adsorbs a low-adsorptive component at a predetermined ratio is applied to the entire interior of the fuel gas adsorption vessel 2. May be filled.

The present invention will be described in more detail based on the following specific examples, but the present invention is not limited to the following examples.

(Example 1)
The device shown in FIG. 2 was used as the fuel gas adsorption device 11, and the fuel gas adsorption cartridge 12 was prepared by filling the fuel gas adsorption container 13 with 1500 g of bromine-impregnated activated carbon (average particle size: 4 mm, average pore size: 15 Å). . At this time, 60 g (4% by volume) of activated carbon having CO ₂ adsorbed in advance was filled in the downstream side of the fuel gas adsorption container 13 with respect to the flow direction of the fuel gas. As the CO ₂ sensor 17, a WINSEN "MH-Z14A" CO ₂ sensor was used.

In such a fuel gas adsorption device 11, propane gas G is circulated as a fuel gas at a flow rate of 10 L/min, and the calorie of the exhaust gas from the outlet of the fuel gas adsorption cartridge 12 is measured by the calorimeter 16 and the CO ₂ sensor is measured. FIG. 3 shows the result of measuring the concentration of CO ₂ gas by 17 together with the calorie of propane gas G flowing into the fuel gas adsorption cartridge 12 . Also, FIG. 4 shows the transition of the concentration of CO ₂ gas in FIG. 3 for 12 minutes.

(Example 2)
The fuel gas adsorption device 11 is configured in the same manner as in Example 1, except that 410 g (27% by volume) of activated carbon on which CO ₂ has been adsorbed in advance is filled on the downstream side. The calorie of the exhaust gas from the outlet of the fuel gas adsorption cartridge 12 is measured by the calorimeter 16 and the concentration of the CO ₂ gas is measured by the CO ₂ sensor 17, and the result is flowed into the fuel gas adsorption cartridge 12. It is shown together with the calorie of propane gas G in FIG. Moreover, the transition of the concentration of CO ₂ gas in FIG. 3 is also shown in FIG.

As is clear from FIGS. 3 and 4, the calorie of the exhaust gas from the outlet of the fuel gas adsorption cartridge 12 is almost "0" until about 15 minutes have passed. , it can be seen that the propane gas G can be adsorbed. On the other hand, the CO ₂ concentration of the exhaust gas begins to rise after about 10 minutes, and starts to decrease after about 13 minutes, and along with this, the calorie of the exhaust gas rises after about 15 minutes (propane gas G leaks). _{At first} , it can be confirmed that the fuel gas adsorption cartridge ₁₂ has passed through. It can be seen that it is possible to determine when to replace the fuel gas adsorption cartridge 12 based on the behavior of the gas. As described above, the time required for the fuel gas adsorption cartridge ₁₂ to break through varies depending on the concentration and flow rate of the fuel gas such as propane gas G. can be set as appropriate.

The fuel gas adsorption apparatus of the present invention as described above is capable of judging the break-through timing of the transient type fuel gas adsorption cartridge, and the town gas alternative propane gas generator and the transient type fuel gas adsorption cartridge can be used. For exchanging gas flow meters for fuel gas, for purging fuel gas when constructing new gas pipes, for releasing VOCs into the atmosphere during the ventilation process during regular maintenance of VOC tanks, for removing hydrogen sulfide odors at the outlet of septic tanks, For prevention of atmospheric diffusion of corrosive gas and sulfur-based gas during replacement work of activated carbon adsorption towers, and for filling gas mainly containing sulfur in sewage manholes when ports are opened (for example, sulfur-based gases such as hydrogen sulfide, methyl mercaptan, etc.) It can be applied to various uses such as the removal of poison gas), and its industrial utility value is great.

1, 12 fuel gas adsorption cartridges 2, 13 fuel gas adsorption vessel 3 inlet (gas inflow member)
4 outlet (exhaust pipe)
5A, 5B spacer members 6, 7 fine-grain porous gas adsorbent 11 fuel gas adsorption device 14 inlet 14A fuel gas supply pipe 15 outlet 15A discharge pipe 16 calorimeter 17 CO ₂ sensor (sensor for components with low adsorption )
18 Gas cylinder 19 Flow meter 20 Open/close valve G Propane gas (fuel gas)
G1 exhaust gas

Claims (6)

A fuel gas adsorption container having an inlet and an outlet is filled with a fine-grained porous gas adsorbent, and at least a part of the fine-grained porous gas adsorbent contains a component having a lower adsorptive property than the fuel gas to be adsorbed. a fuel gas adsorption cartridge that adsorbs
and a sensor for the low-adsorptive component provided on the outlet side of the fuel gas adsorption container. 2. The fuel gas adsorption device according to claim 1 , wherein the fuel gas to be adsorbed is methane gas, propane gas, butane gas, or a mixed gas containing these gases as main components. 3. The fuel gas adsorption device according to claim 1 , wherein said fine-grained porous gas adsorbent is selected from carbonaceous porous material, zeolite, silica gel and porous alumina. 4. The fine - grained porous gas adsorbent that adsorbs the low - adsorptive component is arranged downstream of the fuel gas adsorption container with respect to the flow direction of the fuel gas. 3. The fuel gas adsorption device according to claim 1. 5. The fuel gas adsorption device according to claim 4 , wherein the fine-grained porous gas adsorbent that adsorbs the low-adsorptive component accounts for 2 to 50% by volume of the total amount of the fine-grained porous gas adsorbent. . A fuel gas adsorption container having an inlet and an outlet is filled with a fine-grained porous gas adsorbent, and at least a part of the fine-grained porous gas adsorbent contains a component having a lower adsorptive property than the fuel gas to be adsorbed. The gas to be adsorbed is circulated from the inlet side of the fuel gas adsorption container of the fuel gas adsorption cartridge that adsorbs the A method for judging the replacement timing of a fuel gas adsorption cartridge, which comprises measuring the low adsorptive component and predicting the gas adsorption capacity of the fuel gas adsorption cartridge.

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