JP2021049482A - Method for production of refined gas, and gas purifier - Google Patents

Abstract

To provide a gas purifier which does not lower a production efficiency when producing valuable materials such as ethanol from an obtained refined gas and also prevents bubbling occurrence or the like in a fermentation tank filled with an organic catalyst when using the organic catalyst in the production of valuable materials.SOLUTION: A gas purifier comprises: at least one adsorption tower 21, 22 filled with an adsorbent, purifying a fed gas and renewable by a purge gas; a first feed path 23 feeding a raw material gas derived from waste to the adsorption tower; a hydrogen separator 30 separating and collecting hydrogen from the raw material gas purified in the adsorption tower; and a second feed path 25 feeding the collected hydrogen to the adsorption tower as the purge gas G3.SELECTED DRAWING: Figure 3

Description

The present invention relates to a method for producing a purified gas obtained by purifying a raw material gas derived from waste and a gas purification apparatus.

Various types of waste such as industrial waste and general waste are known to be gasified by thermal decomposition. According to this method, a synthetic gas containing a large amount of carbon monoxide and hydrogen can be obtained by thermally decomposing the waste. Waste-derived gases such as syngas can be used for various purposes. For example, attempts are made to convert them into valuable resources such as ethanol using various catalysts such as organic catalysts such as microbial catalysts and metal catalysts. Has been done. For example, when a microbial catalyst is used, a synthetic gas is supplied to a fermenter having a microbial culture solution, and the synthetic gas is microbially fermented to synthesize ethanol.

Waste contains miscellaneous components, and the gas obtained from waste also contains a large number of impurities. Therefore, the gas derived from waste removes impurities before it is converted into valuable resources by an organic catalyst or the like. Is common. For example, in Patent Document 1, in a synthetic gas purification treatment method including a step of removing gaseous impurities in which a synthetic gas is brought into contact with an adsorbent, the step of removing gaseous impurities is described by a pressure swing adsorption method (PSA: Pressure Swing Attachment) and a temperature. It is disclosed that the swing adsorption method (TSA: Thermal Swing Addition) or the like is used.

Here, the temperature swing adsorption method is a method in which the adsorbent is repeatedly used by adsorbing and regenerating the substance on the adsorbent by changing the temperature. Specifically, at the time of adsorption, the gas to be purified is cooled to a low temperature and passed through the adsorbent, and at the time of regeneration, the heated purge gas is passed through the adsorbent to desorb the substance adsorbed by the adsorbent. .. As the purge gas, an inert gas such as nitrogen gas is generally used.

Further, for example, Patent Document 2 discloses a hydrogen gas purification apparatus using a temperature swing adsorption method. The hydrogen gas purification apparatus of Patent Document 2 has one or more adsorption towers filled with an adsorbent that adsorbs carbon monoxide, a derivation route for taking out the hydrogen gas purified by the adsorption tower, and a branch branched from the derivation route. It is disclosed that a part of the hydrogen gas purified by the adsorption tower is supplied to the adsorption tower via a branch path, and the adsorption tower is regenerated by the hydrogen gas.

JP-A-2018-58042 JP-A-2017-77534

As described above, when nitrogen gas is used as the purge gas in the temperature swing adsorption method, nitrogen gas remains inside the adsorption tower after regeneration. Therefore, when the adsorbent is regenerated and then the raw material gas derived from waste is passed through the adsorption tower for gas purification, a relatively large amount of nitrogen gas is discharged from the adsorption tower together with the refined gas. Therefore, the ratio of the amount of nitrogen gas that is inactive to the catalyst becomes high in the raw material gas, which causes a problem that the production efficiency of valuable resources decreases. Further, when a microbial catalyst is used, a large amount of nitrogen gas, which is an inert gas, is blown into the fermenter to cause foaming, which lowers the production efficiency and increases the load of cleaning maintenance.

On the other hand, in the method of generating valuable resources from the gas derived from waste, as in Patent Document 2, a part of the gas (hydrogen gas) purified by the adsorption tower that performs temperature swing adsorption is used when the adsorption tower is regenerated. When used as it is as a purge gas, it is possible to prevent a large amount of nitrogen gas, which is inert to the catalyst, from coming into contact with the catalyst. However, a large amount of refined gas containing carbon atoms such as carbon monoxide will be discarded, and a decrease in the production of valuable resources will be unavoidable.

Therefore, the present invention lowers the production efficiency when producing valuable resources such as ethanol from the obtained refined gas in the refined gas production method and the gas purification apparatus for purifying the gas derived from waste to obtain the refined gas. In addition, when an organic catalyst is used in the production of valuable resources, the purpose is to prevent foaming that occurs in a fermenter filled with the organic catalyst.

The gist of the present invention is as follows.
[1] A method for producing a purified gas, which obtains a purified gas by at least purifying a raw material gas derived from waste in at least one adsorption tower filled with an adsorbent.
The process of purifying the raw material gas derived from waste by passing it through the adsorption tower, and
A step of separating and recovering at least a part of hydrogen from the raw material gas, and
A step of passing the recovered hydrogen through the adsorption tower, desorbing the substance adsorbed by the adsorbent, and regenerating the adsorption tower.
A method for producing a purified gas.
[2] At least two adsorption towers are provided.
The method for producing a purified gas according to the above [1], wherein the recovered hydrogen is passed through at least one of the adsorption towers while the raw material gas derived from waste is passed through the at least one of the adsorption towers.
[3] The method for producing a purified gas according to the above [1] or [2], wherein a temperature swing adsorption device having the adsorption tower is provided.
[4] The method for producing a purified gas according to any one of [1] to [3] above, wherein the recovered hydrogen is heated and passed through the adsorption tower.
[5] The method for producing a purified gas according to any one of [1] to [4] above, wherein the step of separating and recovering the hydrogen is performed on a hydrogen separation membrane.
[6] Further provided with a step of purifying the raw material gas by a pressure swing adsorption device.
The method for producing a purified gas according to any one of [1] to [5] above, wherein the raw material gas purified by the pressure swing device is passed through the adsorption tower and further refined.
[7] The method for producing a purified gas according to any one of [1] to [6] above, wherein the recovered hydrogen is used to desorb the pressure swing adsorption device.
[8] Further provided with a step of deoxidizing the raw material gas.
The method for producing a purified gas according to any one of the above [1] to [7], wherein at least a part of hydrogen is separated and recovered from the deoxidized gas.
[9] The method for producing a purified gas according to any one of the above [1] to [8], wherein at least a part of hydrogen is separated and recovered from the raw material gas purified by passing through the adsorption tower.
[10] The item according to any one of [1] to [9] above, wherein the inert gas is mixed with the separated and recovered hydrogen so as to be equal to or less than the ratio of the inert gas in the raw material gas. Method of producing refined gas.
[11] A method for producing valuable resources, wherein the purified gas obtained by the method for producing purified gas according to any one of [1] to [10] above is brought into contact with an organic catalyst to obtain valuable resources.
[12] An adsorbent-filled, purified gas supplied, and at least one adsorbent that can be regenerated by purging gas.
The first supply path for supplying the raw material gas derived from waste to the adsorption tower, and
A hydrogen separator that separates and recovers at least a part of hydrogen from the raw material gas,
A gas purification apparatus including a second supply path for supplying the recovered hydrogen to the adsorption tower as a purge gas.
[13] It has at least two adsorption towers and has
The gas purification apparatus according to the above [12], wherein the first supply path can supply the raw material gas to each adsorption tower, and the second supply path can supply the purge gas to each adsorption tower.
[14] The gas purification apparatus according to the above [12] or [13], which comprises a temperature swing adsorption device having the adsorption tower.
[15] The gas purification apparatus according to any one of [12] to [14] above, which comprises a heating means for heating the recovered hydrogen.
[16] The gas purification device according to any one of [12] to [15] above, wherein the hydrogen separation device is a hydrogen separation membrane.
[17] The gas purification apparatus according to any one of [12] to [16] above, wherein a pressure swing adsorption device is provided in front of the adsorption tower.
[18] The gas purification apparatus according to the above [17], which includes a third supply path for supplying the recovered hydrogen to the pressure swing adsorption device.
[19] The gas purification apparatus according to any one of [12] to [18] above, which includes an oxygen scavenger provided in front of the hydrogen separation apparatus.
[20] The gas purification device according to any one of [12] to [19] above, wherein the hydrogen separation device is provided after the adsorption tower.
[21] The gas purification apparatus according to any one of [12] to [20] above, which comprises a gas supply path for mixing the recovered hydrogen with another gas.
[22] A valuable resource including the gas purification apparatus according to any one of the above [12] to [21] and a valuable resource generating unit having an organic catalyst for contacting with the purified gas obtained by the gas purification apparatus. manufacturing device.

In the present invention, in a refined gas production method and a gas purification apparatus for purifying a gas derived from waste to obtain a refined gas, the production efficiency when producing valuable resources such as ethanol from the obtained refined gas is not lowered. In addition, when an organic catalyst is used in the production of valuable resources, it is possible to prevent foaming that occurs in a fermenter filled with the organic catalyst.

It is a schematic diagram which shows the whole structure of the valuables manufacturing apparatus which has the gas refining apparatus which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows the detail of the valuables generation part in 1st Embodiment. It is a schematic diagram which shows the detail of the temperature swing adsorption apparatus in 1st Embodiment. It is a schematic diagram which shows the whole structure of the valuables manufacturing apparatus which has the gas refining apparatus which concerns on 2nd Embodiment of this invention. It is a schematic diagram which shows the whole structure of the valuables manufacturing apparatus which has the gas refining apparatus which concerns on 3rd Embodiment of this invention. It is a schematic diagram which shows the detail of the pressure swing suction apparatus in 3rd Embodiment.

Next, the present invention will be described with reference to the drawings.
[First Embodiment]
FIG. 1 shows a valuable resource manufacturing apparatus having a gas refining apparatus according to the first embodiment of the present invention.
As shown in FIG. 1, the valuable resource manufacturing apparatus includes a gas refining apparatus 10, a raw material gas generation facility 11, and a valuable resource generation unit 12. The raw material gas generation facility 11 is a facility for generating the raw material gas G1 which is a waste-derived gas. The raw material gas G1 generated by the raw material gas generation facility 11 is introduced into the gas refining apparatus 10. The gas purification apparatus 10 purifies by removing impurities from the introduced raw material gas G1 to obtain a purified gas G2. The refined gas G2 produced by the gas purification apparatus 10 is introduced into the valuable resource generation unit 12. The valuable resource generation unit 12 generates valuable resources such as ethanol from the introduced purified gas G2.

<Raw material gas generation equipment>
The raw material gas generation facility 11 is a facility that gasifies the waste and purifies the raw material gas derived from the waste. For gasification of waste, for example, a gasification furnace may be used. The gasification furnace is a furnace that burns (incompletely burns) a carbon source, and examples thereof include a shaft furnace, a kiln furnace, a fluidized bed furnace, and a gasification reforming furnace. The temperature at which the waste is gasified into the raw material gas is not particularly limited, but is usually 100 to 2500 ° C, preferably 200 to 2100 ° C.

The raw material gas G1 obtained by gasifying the waste is preferably a synthetic gas containing carbon monoxide and hydrogen, but may further contain at least one of carbon dioxide, oxygen, and nitrogen. The raw material gas G1 contains water and contains gaseous impurities such as hydrogen sulfide, hydrogen chloride, blue acid, ammonia, NOx, SOx, acetylene and BTEX (benzene, toluene, ethylbenzene, xylene), solids such as sous and tar, or Contains impurities such as liquid impurities and phase transition impurities. Most of the phase-transferable impurities are in the gas phase when they are delivered from the raw material gas generation facility 11, but some or all of them undergo a phase transition in the transportation process to the valuable resource generation unit 12. Impurities that can become (excluding water), and examples thereof include sublimable substances such as naphthalene, 1-naphthol, and 2-naphthol.

When the raw material gas G1 is a synthetic gas, it contains carbon monoxide and hydrogen. Further, the raw material gas G1 preferably contains carbon monoxide in an amount of 0.1% by volume or more and 80% by volume or less, and hydrogen in an amount of 0.1% by volume or more and 80% by volume or less. Further, the synthetic gas constituting the raw material gas G1 may contain carbon dioxide. Carbon dioxide is preferably contained in the raw material gas G1 in an amount of 0.1% by volume or more and 70% by volume or less.
The carbon monoxide concentration in the raw material gas G1 is preferably 10% by volume or more and 70% by volume or less, and more preferably 20% by volume or more and 55% by volume or less. The hydrogen concentration in the raw material gas G1 is preferably 10% by volume or more and 70% by volume or less, and more preferably 20% by volume or more and 55% by volume or less.

The carbon dioxide concentration in the raw material gas G1 is not particularly limited, but is preferably 0.1% by volume or more and 40% by volume or less, and more preferably 0.3% by volume or more and 30% by volume or less. The carbon dioxide concentration is particularly preferably lowered when ethanol is produced using an organic catalyst, and from such a viewpoint, it is more preferably 0.5% by volume or more and 25% by volume or less.
The nitrogen concentration in the raw material gas G1 is usually 40% by volume or less, preferably 1% by volume or more and 20% by volume or less.
The oxygen concentration in the raw material gas G1 is usually 5% by volume or less, preferably 1% by volume or less. Further, the oxygen concentration should be as low as possible, and may be 0% by volume or more. However, in general, oxygen is inevitably contained in many cases, and the oxygen concentration is practically 0.01% by volume or more.

For the concentrations of carbon monoxide, carbon dioxide, hydrogen, nitrogen and oxygen in the raw material gas G1, the combustion conditions such as the type of waste, the gasification temperature in the raw material gas generation process, and the oxygen concentration of the supply gas during gasification are appropriately changed. By doing so, the range can be set to a predetermined range. For example, if you want to change the concentration of carbon monoxide or hydrogen, change to waste with a high ratio of hydrocarbons (carbon and hydrogen) such as waste plastic, and if you want to reduce the nitrogen concentration, oxygen in the raw material gas generation facility 11. There is a method of supplying a high-concentration gas.
Further, the concentration of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen may be appropriately adjusted in the raw material gas G1. The concentration may be adjusted by adding at least one of these components to the raw material gas G1.
The volume% of each substance in the raw material gas in the raw material gas G1 described above means the volume% of each substance in the raw material gas immediately before being introduced into the temperature swing adsorption device 20 described later, and the pre-stage treatment described later is performed. In the case, it is the volume% of each substance after the pretreatment.

<Gas purification equipment>
The gas purification device 10 includes a temperature swing adsorption device 20 and a hydrogen separation device 30, and the hydrogen separation device 30 is provided after the temperature swing adsorption device 20. In the present embodiment, at least the raw material gas G1 is purified by the temperature swing adsorption device 20 to obtain the purified gas G2.
In the present specification, the "second stage" means the latter stage along the supply flow of the gas such as the raw material gas, and the "previous stage" means the first stage along the supply flow of the gas such as the raw material gas. The supply flow of the raw material gas means a flow from the introduction of the raw material gas G1 into the gas purification device 10 to the discharge from the gas purification device 10 as the refined gas G2, and in the present embodiment, the raw material gas generation facility 11 It means the flow of gas from the to the valuable resource generation unit 12.

Although not shown, the gas purification apparatus 10 is preferably provided with a pre-stage processing unit in front of the temperature swing adsorption device 20, and the raw material gas G1 is appropriately provided in the pre-stage processing unit before being supplied to the temperature swing adsorption device 20. Pretreatment should be performed. The pretreatment unit removes various impurities, water, carbon dioxide, etc. contained in the raw material gas G1. Of course, the pre-stage processing unit may be omitted.

(Pre-stage processing unit)
Specifically, the pre-stage treatment unit is configured by combining at least one or two or more of a scrubber, a phase transition impurity removing device, a water separation device, a solid-liquid trapping device, a desulfurization device, a pressure swing adsorption device, and the like. If the raw material gas G1 does not have sufficient pressure for supply in the pre-stage processing unit, a blower, a compressor, or the like may be provided.
The scrubber brings a cleaning liquid consisting of water or oil into contact with the raw material gas, and removes at least a part of water-soluble impurities and oil-soluble impurities from the raw material gas G1. Examples of the water-soluble impurities include acid gases such as hydrogen sulfide, hydrogen chloride and blue acid, basic gases such as ammonia, and oxides such as NOx and SOx. Examples of oil-soluble impurities include BTEX, naphthalene, 1-naphthol, 2-naphthol and the like.

The phase transition impurity removing device includes a chiller that cools the raw material gas and a solid separation device that is provided after the chiller and consists of a filter or the like. It is a device that is captured by a solid-state separator.
The water separation device is composed of a chiller or the like, and is a device that agglomerates and liquefies the water contained in the synthetic gas by cooling the raw material gas, and discharges the liquefied water. The chiller of the water separator cools the raw material gas to a lower temperature than the chiller generally used in the phase transition impurity removing device.
The solid-liquid trapping device is composed of a known filter or the like, and removes solid or liquid impurities contained in the raw material gas.

The desulfurization apparatus has a catalyst adsorption tower filled with a catalyst for adsorbing the sulfide compound, and is an apparatus in which the raw material gas is aerated to adsorb the sulfide compound by a catalytic reaction or the like.
The pressure swing adsorber has a suction tower filled with an adsorbent, and by changing the pressure, a purification step of adsorbing and removing impurities on the adsorbent filled in the adsorption tower and adsorbing on the adsorbent It is a device that repeats the regeneration process of removing impurities. In the pressure swing adsorption device, for example, carbon dioxide, gaseous impurities and the like can be removed. The adsorbent used in the pressure swing adsorber may be composed of zeolite, silica gel, activated carbon, etc., but from the viewpoint of efficiently removing carbon dioxide and gaseous impurities, zeolite and silica gel are preferable, and zeolite is more preferable. ..
In the present specification, "removal" means removing at least a part of the target substance to be removed from the raw material gas to reduce the concentration of the target substance in the gas, and completely removes the target substance to be removed. Not limited to removal.

(Temperature swing adsorption device)
The temperature swing adsorption device 20 has an adsorption tower filled with an adsorbent. A first supply path 23 for supplying the raw material gas to the adsorption tower is connected to the adsorption tower. Therefore, the raw material gas G1 is supplied to the adsorption tower via the first supply path 23. The adsorption tower of the temperature swing adsorption device 20 purifies the raw material gas G1 by adsorbing impurities contained in the raw material gas G1 by passing the raw material gas G1 to be refined. The raw material gas (also referred to as “gas G1'”) purified by the temperature swing adsorption device 20 is introduced into the hydrogen separation device 30 via the lead-out path 27.
The adsorption tower of the temperature swing adsorption device 20 can remove gaseous impurities contained in the raw material gas, for example. The gaseous impurities removed by the adsorption tower can be appropriately changed depending on the adsorbent, but preferably contain at least organic impurities such as BTEX.
The adsorbent may be composed of zeolite, silica gel, activated carbon, or the like, but among these, activated carbon is preferable from the viewpoint of efficiently adsorbing and removing organic impurities.

The adsorption tower deteriorates its adsorption performance by adsorbing impurities contained in the raw material gas as described above. Therefore, the adsorption tower passes through the purging gas G3 after passing through the raw material gas for a certain period of time to desorb and regenerate the substance (impurity) adsorbed by the adsorbent. In this embodiment, as will be described later, the hydrogen separated and recovered by the hydrogen separation device 30 is used as the purge gas G3.
The temperature swing adsorption device 20 adsorbs and desorbs impurities by varying the temperature. That is, the temperature of the raw material gas G1 passing through the adsorption tower is lowered, and the impurities contained in the raw material gas G1 are adsorbed by the adsorbent. Further, the purge gas G3 whose temperature is higher than the temperature of the raw material gas G1 at the time of adsorption is passed through the adsorption tower to desorb impurities adsorbed by the adsorbent and regenerate the adsorption tower.
In this way, the adsorption tower can remove impurities with high adsorption performance for a long period of time by repeating adsorption and desorption.
The purge gas G3 may be supplied to the raw material gas generation facility 11 and burned after being used for regenerating the adsorption tower. Since the purge gas G3 containing hydrogen as a main component has high energy, it can be used as a suitable heat source by being burned in a gasification furnace.

(Hydrogen separator)
The hydrogen separation device 30 separates at least a part of hydrogen gas from the gas G1'purified by the temperature swing adsorption device 20. As the hydrogen separation device 30, a known hydrogen separation device can be used, and for example, a pressure swing adsorption device, a temperature swing adsorption device, a hydrogen separation membrane, or the like can be used. Examples of the hydrogen separation membrane include a hydrogen separation polymer membrane and a hydrogen separation metal membrane. Among the above-mentioned hydrogen separation devices, a hydrogen separation membrane is preferable from the viewpoint of obtaining high-purity hydrogen with a simple structure, and a hydrogen separation polymer membrane is more preferable from the viewpoint of durability and the like, and further preferable. Is a polyamide-based polymer film.

In the hydrogen separation device 30, it is preferable to separate and recover a part of the hydrogen contained in the gas G1'purified by the temperature swing adsorption device 20. The raw material gas G1 derived from waste often contains a relatively large amount of hydrogen gas, but by separating and removing a part of hydrogen with a hydrogen separator, it becomes easy to make the amount of hydrogen in the purified gas G2 appropriate. Further, even if only a part of the hydrogen contained in the gas G1'is recovered, a sufficient amount of hydrogen gas can be supplied to regenerate the adsorption tower of the temperature swing adsorption device 20.

The amount of hydrogen separated and recovered in the hydrogen separation device 30 is not particularly limited, but is preferably 15% by volume or less of the hydrogen contained in the gas G1'. When the amount of hydrogen separated by the hydrogen separator 30 is 15% by volume or less, it becomes easy to make the amount of hydrogen in the purified gas G2 appropriate. From the above viewpoint, the amount of hydrogen separated and recovered is more preferably 10% by volume or less, and further preferably 5% by volume or less.
Further, from the viewpoint of recovering a certain amount or more of hydrogen and appropriately regenerating the adsorption tower of the temperature swing adsorption device 20, the amount of hydrogen is preferably 0.1% by volume or more, preferably 0.2% by volume or more. More preferably, 0.5% by volume or more is further preferable.

Further, the hydrogen separated and recovered may be composed of hydrogen alone, but may contain other components as long as the hydrogen concentration (purity) is higher than the hydrogen concentration of the gas G1'. Other components include gas components other than hydrogen such as carbon monoxide, carbon dioxide, and nitrogen.
The purity of the separated and recovered hydrogen is preferably 80% by volume or more, more preferably 90% by volume or more, further preferably 95% by volume or more, and preferably 99% by volume or more. Even more preferable. Further, the higher the purity of the separated and recovered hydrogen, the better, and it may be 100% by volume or less. The separated and recovered hydrogen is used as the purge gas G3 and then discarded as described later. By increasing the purity, the amount of carbon monoxide and other carbon sources contained in the raw material gas G1 can be reduced.

Further, the separated and recovered hydrogen can be used as it is as a purge gas, or can be appropriately mixed with another gas such as an inert gas (for example, nitrogen) to change the hydrogen ratio and used as a purge gas. Therefore, a gas supply path (not shown) for mixing another gas (inert gas) with the recovered hydrogen may be provided, and the gas supply path is connected to, for example, a second supply path 25 described later. Good.
When the inert gas (for example, nitrogen gas) is less than 100% by volume, foaming can be suppressed as compared with the case of purging with a gas of 100% by volume of nitrogen gas. Further, when handling a raw material gas having a large fluctuation in the composition of waste such as MSW, if the amount of hydrogen contained in the gas becomes extremely small, the amount of hydrogen used as a purge gas can be suppressed.

Further, when the amount of the inert gas such as nitrogen contained in the purge gas G3 is larger than the amount of the inert gas contained in the gas G1', foaming is likely to occur, so that the ratio of the inert gas such as nitrogen in the purge gas G3 ((Inert gas concentration vol% of purge gas G3)-(Inert gas concentration vol% of gas G1')) / (Inert gas concentration vol% of gas G1') × 100 (%) The value calculated in is 50% or less, preferably 20% or less, more preferably 10% or less, and further preferably 0% or less.

Further, the hydrogen separation device 30 generally requires heating of the gas G1'when separating hydrogen from the gas G1', but when a blower, a compressor, or the like is provided in the pretreatment section, the compressed gas is used. It may be heated by heat exchange of.

The gas purification device 10 includes a second supply path 25 that connects the hydrogen separation device 30 and the adsorption tower of the temperature swing adsorption device 20 and supplies the hydrogen recovered by the hydrogen separation device 30 to the adsorption tower. Therefore, the hydrogen recovered by the hydrogen separation device 30 is supplied as the purge gas G3 to the adsorption tower of the temperature swing adsorption device 20 via the second supply path 25. That is, the hydrogen recovered by the hydrogen separation device 30 passes through the adsorption tower of the temperature swing adsorption device 20 to desorb the substance adsorbed by the adsorbent and is used to regenerate the adsorption tower.

(Valuable resource generator)
The gas purification device 10 includes an introduction path 31 capable of introducing the gas from which hydrogen has been separated by the hydrogen separation device 30 into the valuable resource generation unit 12. The gas from which hydrogen has been separated by the hydrogen separation device 30 is appropriately treated by a post-stage treatment unit (not shown) provided in the introduction path 31 as necessary, and then supplied to the valuable resource generation unit 12 as purified gas G2. Will be done. The post-stage processing unit is not particularly limited, and examples thereof include a cleaning device such as a filter. Of course, the post-stage processing unit may be omitted.

The valuable resource generation unit 12 has a catalyst such as an organic catalyst or a metal catalyst. In the valuable resource generation unit 12, the purified gas G2 comes into contact with a catalyst such as an organic catalyst or a metal catalyst and is converted into valuable resources. The valuable resource is not particularly limited as long as it is an organic compound that can be converted from synthetic gas, but ethanol is preferable. Ethanol can be easily synthesized from hydrogen and carbon monoxide contained in syngas. Further, as the catalyst used in the valuable resource generation unit 12, an organic catalyst is preferable. As the organic catalyst, gas-utilizing microorganisms are preferably used.
When converting to ethanol using gas-utilizing microorganisms, synthetic gas is supplied to the inside of a fermenter filled with gas-utilizing microorganisms, and the synthetic gas is microbially fermented in the microbial fermenter to produce ethanol. To do.

FIG. 2 shows a schematic diagram showing the configuration of the latter stage of the fermentation layer when a fermentation tank is used. When the valuable resource generation unit 12 includes the fermenter 14, as shown in FIG. 2, a gas measuring device 15 exhausted from the fermenter 14 may be provided in the subsequent stage of the fermenter 14. The measuring device 15 is a device for measuring the component composition of the exhaust gas. The measuring device 15 is not particularly limited as long as it can measure the component composition of the exhaust gas, and is, for example, a gas chromatograph (GC), a mass spectrometer (MS), a gas chromatograph-mass spectrometer (GC-MS), and a Fourier. A conversion infrared spectrophotometer (FTIR) or the like. A separation device 16 may be provided in front of the measuring device 15. The separation device 16 separates water vapor and bubbles from the exhaust gas to prevent them from being mixed into the measuring device 15 and prevent the measuring device from being damaged.

The separation device 16 may be composed of a foam liquid separation device 16A for separating and removing bubbles and liquid, and a vapor separation device 16B for separating and removing vapor from exhaust gas. The foam liquid separation device 16A is not particularly limited as long as it is a device capable of separating and removing bubbles and liquid from the exhaust gas. The foam liquid separation device 16A is, for example, a device capable of cutting a foam to separate it into a gas and a liquid, and removing the liquefied foam and the liquid contained separately from the foam. Examples of such a device include a bubble removing filter and a defoaming device. Specific examples of the bubble removing filter include, but are not limited to, an H600 series in-line filter (manufactured by Hamlet Co., Ltd.). The foam liquid separation device 16A and the foam liquid separation device 16A may have one or two or more of each. By preparing a plurality of them, it is possible to deal with cases where the composition fluctuation is extremely large.

As described above, in the present embodiment, when hydrogen in the gas G1'is separated and recovered and the hydrogen gas is used as the purge gas G3 of the adsorption tower, the hydrogen gas remains inside the adsorption tower. The remaining hydrogen gas will be supplied to the fermenter in the valuable resource generation unit 12, for example, together with the refined gas. However, since hydrogen gas is active against the organic catalyst inside the fermenter, it is possible to reduce the foaming in the fermenter that is conventionally generated when an inert gas such as nitrogen gas is used as the purge gas. Furthermore, the production efficiency of valuable resources can be improved. Here, foam blowing means that bubbles are generated in the fermenter, which raises the liquid level in the fermenter and allows the liquid and bubbles to flow into the subsequent stage of the fermenter. As a result, problems such as equipment failure of the measuring device in the subsequent stage and a decrease in the productivity of valuable resources due to a decrease in the amount of liquid in the fermenter occur.

Further, by separating hydrogen with the hydrogen separation device 30, it is possible to reduce the hydrogen concentration in the purified gas G2, so that it is possible to prevent a decrease in production efficiency due to an excessively high hydrogen concentration in the purified gas. Furthermore, while the gas containing the carbon source is used for the generation of valuable resources without being separated, it is also possible to prevent the gas composition supplied to the valuable resource generation unit 12 from fluctuating by appropriately separating hydrogen. Since this is possible, it is possible to prevent a decrease in reactivity and an increase in the amount of by-products due to fluctuations in the gas composition.
Further, in the present embodiment, since the hydrogen separation device is provided after the temperature swing adsorption device (adsorption towers 21 and 22 described later), a part of the barge gas (hydrogen gas) mixed in the raw material gas is separated by the hydrogen separation device. Since it can be recovered, it is possible to effectively prevent excessive mixing of the barge gas G3 into the valuable resource generating unit 12.
Further, since hydrogen gas has small molecules and easily permeates through micropores, the adsorption tower can be regenerated in a short time by being used as purge gas G3.

(Details of temperature swing adsorption device)
FIG. 3 is a schematic view for showing the details of the temperature swing adsorption device 20. Hereinafter, the temperature swing adsorption device 20 will be described in more detail with reference to FIG. In the following description, an example in which the temperature swing adsorption device 20 has two adsorption towers will be described.
As shown in FIG. 3, the temperature swing adsorption device 20 includes first and second adsorption towers 21 and 22, and a first supply path for supplying the raw material gas G1 to the first and second adsorption towers 21 and 22. 23 is connected. The first supply path 23 is branched into two branch paths 23A and 23B, and the branch paths 23A and 23B are connected to the suction towers 21 and 22. Further, valves 24A and 24B are attached to the branch paths 23A and 23B.
In the first supply path 23, the raw material gas G1 is supplied to the first adsorption tower 21 by opening the valve 24A and closing the valve 24B. Further, when the valve 24B is opened and the valve 24A is closed, the raw material gas G1 is supplied to the second adsorption tower 22.

When the raw material gas G1 is supplied to the first adsorption tower 21 or the second adsorption tower 22, a purification step is performed in each adsorption tower. Specifically, in one of the adsorption towers (either of the first and second adsorption towers 21 and 22) to which the raw material gas G1 is supplied, the raw material gas G1 is introduced into the tower from one end 21A or 22A. .. The temperature of the raw material gas G1 introduced into the adsorption tower is not particularly limited, but may be around room temperature from the viewpoint of facilitating the adsorption of impurities by the adsorbent, for example, 0 to 50 ° C., preferably 5 to 35 ° C.
The raw material gas G1 introduced into the tower passes through the inside of the adsorption towers 21 and 22, and is discharged from the other ends 21B and 22B of the adsorption towers 21 and 22. As the raw material gas G1 passes through the inside of the tower, impurities contained in the raw material gas G1 are adsorbed by the adsorbent. Therefore, the gas discharged from the other ends 21B and 22B of the adsorption towers 21 and 22 is supplied to the hydrogen separation device 30 via the lead-out path 27 as the gas G1'purified by the adsorption towers 21 and 22.

Further, the second supply path 25 for supplying the purge gas G3 to the temperature swing adsorption device 20 is branched into two branch paths 25A and 25B, and valves 26A and 26B are attached to the branch paths 25A and 25B, respectively. ing. The branch paths 25A and 25B are connected to the other ends 21B and 22B of the suction towers 21 and 22, respectively.
When the valve 26A is opened and the valve 26B is closed in the second supply path 25, the purge gas G3 is supplied to the first suction tower 21. Further, when the valve 26B is opened and the valve 26A is closed, the purge gas G3 is supplied to the second suction tower 22. Further, a heating means 29 is provided in the second supply path 25. Therefore, the purge gas G3 is heated by the heating means 29 and then passes through either the first adsorption tower 21 or the second adsorption tower 22. As the heating means 29, a known heater can be used.

By introducing the purge gas G3 into the first adsorption tower 21 or the second adsorption tower 22, the regeneration step is performed in each adsorption tower. Specifically, in one of the adsorption towers (one of the first and second adsorption towers 21 and 22) to which the purge gas G3 is supplied, the purge gas G3 is introduced into the tower from the other end 21B or 22B. The purge gas G3 introduced into the tower passes through the inside of the adsorption towers 21 and 22, and is discharged as exhaust gas from the ends 21A and 22A of the adsorption towers 21 and 22 via the exhaust passage 28.
Since the purge gas G3 introduced into the adsorption tower is heated as described above, the adsorbent in contact with the purge gas G3 is heated, and as a result, substances adsorbed on the adsorbent (impurities adsorbed in the purification step, etc.) Is detached. The desorbed substance is discharged from the exhaust passage 28 as exhaust gas together with the purge gas G3.
Here, the temperature of the purge gas G3 inside the adsorption tower is, for example, 80 to 250 ° C, preferably 100 to 200 ° C. By setting the temperature of the purge gas G3 to 80 ° C. or higher, the substance adsorbed on the adsorbent can be easily desorbed. Further, by setting the temperature to 250 ° C. or lower, the adsorbent can be regenerated without heating the purge gas more than necessary.

In addition, the regeneration step may generally proceed in parallel with the purification step. Specifically, it is preferable to pass the waste-derived raw material gas G1 through one adsorption tower and the purge gas G3 through the other adsorption tower. Therefore, for example, when the raw material gas G1 is passed through the first adsorption tower 21 by opening the valve 24A and closing the valve 24B, the second adsorption tower is opened by opening the valve 26B and closing the valve 26A. It is preferable to pass the purge gas G3 through 22. Further, when the raw material gas G1 is passed through the second adsorption tower 22 by opening the valve 24B and closing the valve 24A, the valve 26A is opened and the valve 26B is closed to form the first adsorption tower 21. It is preferable to pass the purge gas G3.

Further, in each of the first and second adsorption towers 21 and 22, the opening and closing of each valve may be repeated, and the above-mentioned purification step and regeneration step may be alternately repeated. In the present embodiment, a plurality of adsorption towers are provided in this way, and the raw material gas G1 is sequentially purified by the plurality of adsorption towers, so that the raw material gas is continuously purified by the adsorption towers.
The purification step performed in each adsorption tower may be continuously performed for a predetermined time, for example, 2 to 96 hours, preferably 4 to 72 hours.
On the other hand, the regeneration step may be carried out continuously for the same time as the purification step, but it is preferably carried out continuously for a shorter time than the purification step carried out in parallel. Specifically, for example, it may be carried out for 1 to 40 hours, preferably 2 to 20 hours. Even if the time required for the regeneration step is shorter than that for the purification step, the adsorbent can generally be sufficiently desorbed. Further, in the present embodiment, by using hydrogen gas as the purge gas, the adsorbent can be desorbed in a shorter time as described above.
After the regeneration step is performed, the adsorption towers 21 and 22 may be cooled by flowing a purge gas G3 or the like having a temperature equal to or lower than the predetermined temperature.

[Second Embodiment]
Next, the refined gas apparatus and the method for producing the purified gas according to the second embodiment of the present invention will be described with reference to FIG. In the following, the same members as those in the first embodiment are designated by the same reference numerals, the description thereof will be omitted, and the differences from the first embodiment will be described.
The refined gas device 40 in the second embodiment further includes a deoxidizing device 41. As shown in FIG. 4, the oxygen scavenger 41 is provided after the temperature swing adsorption device 20 (that is, the adsorption towers 21 and 22) and before the hydrogen separation device 30. That is, the oxygen scavenger 41 is provided in the middle of the lead-out path 27. The oxygen scavenger 41 deoxidizes the gas G1'purified by the temperature swing adsorption device 20 and supplies the deoxidized gas G1'to the hydrogen separation device 30.
Examples of the deoxidizing device 41 include a separating device having a deoxidizing catalyst such as a copper catalyst or a palladium catalyst. A copper catalyst is preferably used as the deoxidizing catalyst. Deoxygenation can be performed efficiently by using a separation device having a copper catalyst.

The raw material gas G1 and the gas G1'purified by the temperature swing adsorption device 20 may contain oxygen gas. If oxygen gas is mixed into the hydrogen (purge gas G3) separated by the hydrogen separation device 30, it may explode. However, in the present embodiment, the hydrogen separation device is subjected to the deoxidization treatment in the preceding stage of the hydrogen separation device 30. It is possible to prevent the hydrogen separated by 30 from exploding. Therefore, in the present embodiment, it is possible to provide a more safe refined gas apparatus and a method for producing a refined gas.

[Third Embodiment]
Next, the refined gas apparatus and the method for producing the purified gas according to the third embodiment of the present invention will be described with reference to FIG. In the following description, the same members as those in the second embodiment are designated by the same reference numerals, the description thereof will be omitted, and the differences from the second embodiment will be described below.
The refined gas device 50 of the present embodiment further includes a pressure swing adsorption device 60 as shown in FIG. The pressure swing suction device 60 is provided in front of the temperature swing suction device 20 (that is, the suction towers 21 and 22). As described in the first embodiment, the pressure swing suction device 60 constitutes at least a part of the pre-stage processing unit, and therefore, also in this embodiment, a device other than the pressure swing suction device 60 (not shown) as the pre-stage processing unit. May be provided as appropriate.

Further, a third supply path 53 is provided in addition to the second supply path 25 capable of supplying hydrogen gas from the hydrogen separation device 30, and the hydrogen gas separated and recovered by the hydrogen separation device 30 is the second and third. The purge gas G3 is supplied to the temperature swing adsorption device 20 and the pressure swing adsorption device 60 via the supply paths 25 and 53, respectively.
In the temperature swing adsorption device 20, as described in the first embodiment, impurities in the raw material gas G1 are removed and purified by the adsorption tower, and the adsorption tower adsorbing the impurities is regenerated by the purge gas G3.

(Pressure swing suction device)
The pressure swing adsorption device 60 has an adsorption tower filled with an adsorbent. The raw material gas G1 is supplied to the pressure swing adsorption device 60 from the raw material gas generation facility 11 side via the fourth supply path 54.
The adsorption tower of the pressure swing adsorption device 60 purifies the raw material gas G1 by adsorbing impurities contained in the raw material gas G1 by passing the raw material gas G1 to be refined. The gas (raw material gas G1) purified by the pressure swing adsorption device 60 is supplied to the temperature swing adsorption device 20 via the first supply path 23, and is further refined by the adsorption tower of the temperature swing adsorption device 20.

The adsorption tower of the pressure swing adsorption device 60 can remove, for example, gaseous impurities, carbon dioxide, etc. contained in the raw material gas. The gaseous impurities removed by the adsorption tower can be appropriately changed depending on the adsorbent, but preferably contain at least organic impurities such as BTEX. Therefore, by providing the pressure swing adsorption device 60, the amount of impurities in the obtained purified gas G2 can be further reduced. In addition, the amount of carbon dioxide in the raw material gas G1 can be reduced.
The adsorbent used in the pressure swing adsorber 60 may be composed of zeolite, silica gel, activated carbon, etc. Among these, silica gel and zeolite are used from the viewpoint of efficiently removing carbon dioxide and gaseous impurities. Is preferable, and zeolite is more preferable.

The adsorption tower of the pressure swing adsorption device 60 deteriorates its adsorption performance by adsorbing impurities contained in the raw material gas. Therefore, it is preferable that the adsorption tower desorbs the substance (impurity) adsorbed on the adsorbent after passing the raw material gas G1 for a certain period of time by the purge gas G3 (hydrogen gas). The pressure swing adsorption device 60 adsorbs and desorbs impurities by varying the pressure.
More specifically, when the raw material gas G1 passes through the adsorption tower, the inside thereof is set to, for example, normal pressure or a pressure higher than normal pressure, and impurities contained in the raw material gas G1 are adsorbed by the adsorbent. Further, it is preferable to set the pressure lower than the pressure at the time of adsorption to desorb the impurities adsorbed on the adsorbent.

Here, at the time of desorption, for example, the purge gas G3 (hydrogen gas) supplied from the hydrogen separator 30 is passed through the adsorption tower at a pressure lower than the pressure at which the raw material gas G1 is passed (for example, normal pressure). It is advisable to desorb the substance adsorbed on the adsorbent. Further, the substance adsorbed on the adsorbent may be desorbed by sucking (that is, evacuating) with a vacuum pump or the like to reduce the pressure. In the case of evacuating, it is preferable to supply the purge gas G3 to the inside of the adsorption tower when the adsorption tower is released from the reduced pressure state. Further, in the case of evacuation, the pressure swing suction device 60 is also referred to as a pressure vacuum swing suction device.
The adsorption tower of the pressure swing adsorption device can remove impurities with high adsorption performance for a long period of time by repeating adsorption and desorption as described above.
As the purge gas G3 supplied to the pressure swing adsorption device, a mixture of recovered hydrogen and an inert gas may be used as in the case of the purge gas supplied to the temperature swing adsorption device. Is as above. Further, a gas supply path (not shown) for mixing another gas (inert gas) with the recovered hydrogen may also be connected to the third supply path 53.

FIG. 6 is a schematic view for showing the details of the pressure swing suction device. Hereinafter, the pressure swing suction device 60 will be described in more detail with reference to FIG. In the following description, an example in which the pressure swing suction device 60 is a pressure vacuum swing suction device and has two suction towers will be described. As shown in FIG. 6, the pressure swing suction device 60 includes first and second suction towers 61 and 62, and a fourth supply path for supplying the raw material gas G1 to the first and second suction towers 61 and 62. 54 is connected.

The fourth supply path 54 is branched into two branch paths 54A and 54B, and the branch paths 54A and 54B are connected to one ends 61A and 62B of the first and second suction towers 61 and 62, respectively. Valves 55A and 55B are attached to the branch paths 54A and 54B.
Further, a pressurizing means 63 is provided in the fourth supply path 54, and the raw material gas G1 pressurized by the pressurizing means 63 passes through the branch paths 54A and 54B to the first adsorption tower 61 or the second adsorption tower 61 or the second adsorption. It is supplied to the tower 62. The pressurizing means 63 may be any known one, and for example, a blower device may be used. The raw material gas G1 may be pressurized by the pressurizing means 63, for example, at a gauge pressure of more than 0 kPa and 100 kPa or less, preferably 20 to 80 kPa.
In the fourth supply path 54, the raw material gas G1 is supplied to the first adsorption tower 61 by opening the valve 55A and closing the valve 55B. Further, when the valve 55B is opened and the valve 55A is closed, the raw material gas G1 is supplied to the second adsorption tower 62.

By supplying the raw material gas G1 to the first adsorption tower 61 or the second adsorption tower 62, the purification step is performed in each adsorption tower. Specifically, in one of the adsorption towers (either of the first and second adsorption towers 61 and 62) to which the raw material gas G1 is supplied, the raw material gas G1 is introduced into the tower from one end 61A or 62A. .. The raw material gas G1 introduced into the tower passes through the inside of the adsorption towers 61 and 62 and is discharged from the other ends 61B and 62B of the adsorption towers 61 and 62. As the raw material gas G1 passes through the inside of the tower, impurities contained in the raw material gas G1 are adsorbed by the adsorbent. Therefore, the gas discharged from the other ends 61B and 62B of the adsorption towers 61 and 62 is supplied to the temperature swing adsorption device 20 via the first supply path 23 as the gas purified by the adsorption tower (raw material gas G1). To.

Further, the pressure swing suction device 60 includes a vacuum pump 64, and the vacuum pump 64 is connected to the suction towers 61 and 62 via a decompression passage 65. The decompression passage 65 is branched into two decompression passages 65A and 65B, and the decompression passages 65A and 65B are connected to one ends 61A and 62B of the suction towers 61 and 62. The vacuum pump 64 can suck the inside of the suction towers 61 and 62 to reduce the pressure via the pressure reducing path 65A or the pressure reducing path 65B. Valves 66A and 66B are provided in each of the decompression passages 65A and 65B, respectively.

Further, the third supply path 53 for supplying the purge gas G3 to the pressure swing suction device 60 is branched into two branch paths 53A and 53B, and the branch paths 53A and 53B of the suction towers 61 and 62 It is connected to each of the other ends 61B and 62B. Further, valves 69A and 69B are attached to the branch paths 53A and 53B. When the valve 69A is opened and the valve 69B is closed in the third supply path 53, the purge gas G3 is supplied to the first suction tower 61. Further, when the valve 69B is opened and the valve 69A is closed, the purge gas G3 is supplied to the second suction tower 62.

The first adsorption tower 61 decompresses the pressure by the vacuum pump 64 with the valve 66A opened and the valve 66B closed, and then the valve 66A is also closed to complete the evacuation, and then the valve 53A is opened to purge gas. By supplying G3, a regeneration step is performed in each adsorption tower. Further, also in the second suction tower 62, the regeneration step is similarly performed by opening and closing the valves.
Further, also in the present embodiment, the regeneration step may proceed in parallel with the purification step, similarly to the temperature swing adsorption device 20. Specifically, while passing the waste-derived raw material gas G1 through one of the adsorption towers, the other adsorption tower is sucked by the vacuum pump 64 to reduce the pressure, and then after the vacuuming is completed, the purge gas G3 is used to barge. By doing so, it is advisable to carry out the regeneration step in the other adsorption tower.
Further, in each of the first and second adsorption towers 61 and 62, opening and closing of each valve may be repeated, and the above-mentioned purification step and regeneration step may be alternately repeated. In the present embodiment, a plurality of adsorption towers are provided in this way, and the raw material gas G1 is sequentially purified by the plurality of adsorption towers, so that the raw material gas is continuously purified by the adsorption towers.

The purification steps performed in the suction towers 61 and 62 of the pressure swing suction device 60 may be continuously performed for a predetermined time, for example, 0.1 to 10 minutes, preferably 0.5 to 5 minutes.
Further, each of the first and second adsorption towers 61 and 62 is depressurized by the vacuum pump 64, for example, to less than 0 kPa at a gauge pressure of -101.3 kPa or more, preferably -60 to -98 kPa at a gauge pressure in the regeneration step. To. By setting the pressure inside each adsorption tower within the above range, impurities adsorbed by the adsorbent can be appropriately desorbed. Further, the depressurization by the vacuum pump 64 in each adsorption tower may be performed for the same degree as the purification step or for a shorter time from the viewpoint of the power consumed by the vacuum pump, for example, 0 to 70% of the time of the purification step. , Preferably 5 to 50% shorter time.

In the present embodiment, as described above, hydrogen gas is used as the purge gas G3 not only in the temperature swing adsorption device 20 but also in the pressure swing adsorption device 60. Therefore, it is possible to further reduce the foaming in the fermenter, which is conventionally generated when an inert gas such as nitrogen gas is used as the purge gas. In addition, the production efficiency of valuable resources can be easily improved, and it becomes easy to prevent a decrease in reactivity and an increase in the amount of by-products due to fluctuations in the gas composition. Furthermore, by using hydrogen gas as the purge gas of the pressure swing adsorption device 60, it becomes easy to regenerate the adsorption tower of the pressure swing adsorption device 60 in a short time.

[Other variants]
As described above, the specific description has been made with reference to the embodiments of the present invention, but the present invention is not limited to the above embodiments. Further, various improvements can be made as long as the gist of the present invention is not deviated.
For example, in the temperature swing adsorbent specifically shown in each embodiment, the number of adsorbents was two, but the number of adsorbents in the temperature swing adsorber is not limited to two, and is three or more. May be good. When three or more are provided, the raw material gas G1 may be supplied to only one adsorption tower and purification may be performed by only one adsorption tower, but the raw material gas is supplied to two or more adsorption towers at the same time. The raw material gas G1 may be purified in parallel in two or more adsorption towers. Similarly, the desorption of the adsorption towers may be performed by only one adsorption tower or may be performed in parallel by two or more adsorption towers.
Further, the temperature swing adsorption device may have only one adsorption tower. When there is only one adsorption tower, the purification step of passing the raw material gas G1 through the adsorbent and the regeneration step of passing the purge gas G3 through the adsorption tower may be performed alternately, for example.
Similarly, in the pressure swing suction device described in the third embodiment, the number of suction towers is not limited, and may be three or more, or may be one. Further, the pressure swing suction device is provided with a blower device and a vacuum pump, but these may be omitted as appropriate. Further, in the third embodiment, the oxygen scavenger 41 may be omitted, and in each embodiment, the gas other than the oxygen scavenger 41 is in the rear stage of the temperature swing adsorption device 20 and in the front stage of the hydrogen separation device 30. A device for processing the above may be provided.

Further, the hydrogen (purge gas) separated and recovered by the hydrogen separation device is supplied to the adsorption tower of the temperature swing adsorption device 20 via the second supply path 25, and the hydrogen is stored in the second supply path 25. A device may be provided. When the hydrogen storage device is provided, the recovered hydrogen may be temporarily stored in the hydrogen storage device, and the stored hydrogen may be supplied to the temperature swing adsorption device 20 as purge gas G3 as needed.
Similarly, a hydrogen storage device may be provided in the third supply path 53, whereby the recovered hydrogen is temporarily stored in the hydrogen storage device, and the stored hydrogen is pressured as a purge gas G3 as needed. It is preferable to supply the swing suction device 60.
Further, the hydrogen separation by the hydrogen separator may be performed intermittently or continuously, for example, hydrogen separation may be performed only at the timing when the purge gas is required. Further, when hydrogen separation is continuously performed, hydrogen that is continuously separated and recovered may be stored in a hydrogen storage device, and hydrogen may be appropriately supplied from the hydrogen storage device when purge gas is required.
Further, the hydrogen concentration of the gas G1'may be detected, and the presence or absence of hydrogen separation in the hydrogen separation device and the amount of hydrogen to be separated may be appropriately adjusted according to the detection result.
Further, in each of the above embodiments, the hydrogen separation device 30 is provided after the temperature swing adsorption device 20, but may be provided before the temperature swing adsorption device 20.

Further, in the temperature swing adsorption device 20, the purge gas (hydrogen) is heated by the heating means provided in the second supply passage 25, but the heating means may be, for example, a heater provided in the adsorption tower, and the adsorption tower itself may be used. It may be heated. Further, two or more heating means may be used in combination.
Further, in the pressure swing adsorption device 60, not only the pressure but also the temperature may be varied to perform adsorption and desorption. Similarly, in the swing adsorption device 20, not only the temperature but also the pressure may be varied to perform adsorption and desorption.

Further, in each of the above embodiments, the hydrogen separated by the hydrogen separator is supplied as a purge gas to the adsorption tower of the temperature swing adsorber and used in the regeneration step, but the substance adsorbed by the adsorbent is desorbed. It does not necessarily have to be supplied to the temperature swing adsorber as long as it is used as a purging gas.
For example, in the third embodiment, the temperature swing adsorption device may be omitted, and hydrogen separated by the hydrogen separation device may be supplied only to the adsorption tower of the pressure swing adsorption device. Further, in the first embodiment, a pressure swing adsorption device may be provided instead of the temperature swing adsorption device, and hydrogen separated by the hydrogen separation device may be supplied as a purge gas to the adsorption tower of the pressure swing adsorption device.

10, 40, 50 Gas purification equipment 11 Raw material gas generation equipment 12 Valuables generation unit 14 Fermentation layer 15 Measuring equipment 16 Separation equipment 20 Temperature swing adsorption equipment 21, 61 1st adsorption tower 22, 62 2nd adsorption tower 23 1st supply Road 25 Second supply path 27 Derivation path 28 Exhaust path 29 Heating means 30 Hydrogen separation device 31 Introduction path 32 Heating means 41 Deoxidizer 53 Third supply path 54 Fourth supply path 60 Pressure swing adsorption device 63 Pressurizing means 64 Vacuum Pump G1 Raw material gas G2 Purified gas G3 Purge gas (hydrogen gas)

Claims (22)

A method for producing a purified gas, which obtains a purified gas by at least purifying a raw material gas derived from waste in at least one adsorption tower filled with an adsorbent.
The process of purifying the raw material gas derived from waste by passing it through the adsorption tower, and
A step of separating and recovering at least a part of hydrogen from the raw material gas, and
A step of passing the recovered hydrogen through the adsorption tower, desorbing the substance adsorbed by the adsorbent, and regenerating the adsorption tower.
A method for producing a purified gas. Provide at least two adsorption towers
The method for producing a purified gas according to claim 1, wherein the recovered hydrogen is passed through at least one of the adsorption towers while the raw material gas derived from waste is passed through the at least one of the adsorption towers. The method for producing a purified gas according to claim 1 or 2, wherein a temperature swing adsorption device having the adsorption tower is provided. The method for producing a purified gas according to any one of claims 1 to 3, wherein the recovered hydrogen is heated and passed through the adsorption tower. The method for producing a purified gas according to any one of claims 1 to 4, wherein the step of separating and recovering hydrogen is performed on a hydrogen separation membrane. A step of purifying the raw material gas by a pressure swing adsorption device is further provided.
The method for producing a purified gas according to any one of claims 1 to 5, wherein the raw material gas purified by the pressure swing device is passed through the adsorption tower and further refined. The method for producing a purified gas according to any one of claims 1 to 6, wherein the recovered hydrogen is used to desorb the pressure swing adsorption device. Further provided with a step of deoxidizing the raw material gas,
The method for producing a purified gas according to any one of claims 1 to 7, wherein at least a part of hydrogen is separated and recovered from the deoxidized gas. The method for producing a purified gas according to any one of claims 1 to 8, wherein at least a part of hydrogen is separated and recovered from the raw material gas purified by passing through the adsorption tower. The method for producing a purified gas according to any one of claims 1 to 9, wherein an inert gas is mixed with the separated and recovered hydrogen so as to be equal to or less than the ratio of the inert gas in the raw material gas. .. A method for producing a valuable resource, wherein the purified gas obtained by the method for producing a purified gas according to any one of claims 1 to 10 is brought into contact with an organic catalyst to obtain a valuable resource. An adsorbent-filled, purified gas supplied, and at least one adsorbent that can be regenerated by purge gas.
The first supply path for supplying the raw material gas derived from waste to the adsorption tower, and
A hydrogen separator that separates and recovers at least a part of hydrogen from the raw material gas,
A gas purification apparatus including a second supply path for supplying the recovered hydrogen to the adsorption tower as a purge gas. Has at least two adsorption towers
The gas purification apparatus according to claim 12, wherein the first supply path can supply the raw material gas to each adsorption tower, and the second supply path can supply the purge gas to each adsorption tower. The gas purification apparatus according to claim 12 or 13, further comprising a temperature swing adsorption apparatus having the adsorption tower. The gas purification apparatus according to any one of claims 12 to 14, further comprising a heating means for heating the recovered hydrogen. The gas purification device according to any one of claims 12 to 15, wherein the hydrogen separation device is a hydrogen separation membrane. The gas purification apparatus according to any one of claims 12 to 16, further comprising a pressure swing adsorption device in front of the adsorption tower. The gas purification apparatus according to claim 17, further comprising a third supply path for supplying the recovered hydrogen to the pressure swing adsorption device. The gas purification device according to any one of claims 12 to 18, further comprising a deoxidizing device provided in front of the hydrogen separation device. The gas purification device according to any one of claims 12 to 19, wherein the hydrogen separation device is provided after the adsorption tower. The gas purification apparatus according to any one of claims 12 to 20, further comprising a gas supply path for mixing the recovered hydrogen with another gas. A valuable resource manufacturing apparatus including the gas purification apparatus according to any one of claims 12 to 21 and a valuable resource generating unit having an organic catalyst that is brought into contact with the purified gas obtained by the gas purification apparatus.

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