WO2000048713A1 - Dispositif et procede de traitement de carbure d'hydrogene gazeux dilue contenu dans un gaz de combustion - Google Patents

Dispositif et procede de traitement de carbure d'hydrogene gazeux dilue contenu dans un gaz de combustion Download PDF

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Publication number
WO2000048713A1
WO2000048713A1 PCT/JP2000/000513 JP0000513W WO0048713A1 WO 2000048713 A1 WO2000048713 A1 WO 2000048713A1 JP 0000513 W JP0000513 W JP 0000513W WO 0048713 A1 WO0048713 A1 WO 0048713A1
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Prior art keywords
waste gas
adsorption
gas
adsorbent layer
adsorbent
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PCT/JP2000/000513
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English (en)
Japanese (ja)
Inventor
Hiroshi Tahara
Hiroshi Nochi
Hideki Sakuma
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System Eng Service Co., Ltd.
Shinko Plantech Co., Ltd.
Tsuru, Yoshiko
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Application filed by System Eng Service Co., Ltd., Shinko Plantech Co., Ltd., Tsuru, Yoshiko filed Critical System Eng Service Co., Ltd.
Priority to AU23233/00A priority Critical patent/AU2323300A/en
Priority to KR1020017010446A priority patent/KR20010114209A/ko
Publication of WO2000048713A1 publication Critical patent/WO2000048713A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4143—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged as a mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0446—Means for feeding or distributing gases

Definitions

  • the present invention relates to a method and an apparatus for treating lean gaseous hydrocarbons contained in waste gas, and more particularly to efficiently separating hydrocarbons from waste gas containing harmful gaseous hydrocarbons that cause air pollution. And a detoxifying method and apparatus.
  • harmful gaseous hydrocarbons for example, gaseous substances such as benzene, toluene, methylethylketone, trichloroethylene, and chlorofluorocarbon, which are carcinogenic and are one of the three substances causing air pollution
  • the present invention relates to the treatment of waste gas containing hydrocarbons, and relates to the treatment method and apparatus for reducing the concentration of hydrocarbons to 100 ppm or less (preferably 10 ppm or less) and discharging the hydrocarbons to the atmosphere.
  • Gaseous hydrocarbons such as benzene, toluene, methyl ethyl ketone, trichloroethylene, and chlorofluorocarbon, which are one of the main causes of air pollution, are released into the atmosphere in the United States, Europe, Japan, and other developed countries. Concentrations are strictly regulated by law. Although the level of the regulation value varies depending on the circumstances of each country, in advanced countries other than Japan, for example, benzene is “5 ppm or less”, and in Japan, the Environment Agency Notification No. 5 (February 6, 1997) According to the Japanese government, the regulation was restricted to “30 ppm or less”.
  • a particularly problematic source of such gaseous hydrocarbons is, for example, a large amount of diluted waste gas of about 500 ppm or less generated in a printing factory, a cleaning factory, a painting factory, and the like. Yes, it is waste gas generated not only at factories but also at the time of unloading and unloading from tanks storing them.
  • the method (1) is a mainstream technology in Europe. If the amount of waste gas is large, the adsorption method is used as a polishing step in the treatment after the gas separation membrane method (pressurized membrane method). It is used. In Japan, as disclosed in Japanese Patent Publication No. 4-235658 / Japanese Patent Publication No. Hei 7-2846423, technologies belonging to this field are disclosed.
  • the adsorption method (2) is the most widely used method in the United States.
  • This method is disclosed in Japanese Patent Application Laid-Open No. 57-146687, Japanese Patent Application Laid-Open No. 57-42319, Japanese Patent Publication No. 59-50715, Japanese Patent Publication No. — It is disclosed in Japanese Patent Publication No. 507716 and Japanese Patent Publication No. 2-46663.
  • the adsorption method using activated carbon is the best industrial means. (Note that the catalytic combustion method is also a simple and effective means, but depending on the concentration of gaseous hydrocarbons in the waste gas, there is a danger of an explosion. Strong.)
  • steam is usually used as a purge gas at the time of desorption.
  • the amount of steam required for desorption is about three times the amount of adsorbent used, requiring a large amount.
  • hydrocarbons are entrained and mixed in when this steam condenses into water, so that clear water quality standards require a considerable burden on wastewater treatment facilities such as the activated sludge process.
  • a power scale method is used prior to recovering gaseous hydrocarbons from the purged exhaust gas.
  • One of the solutions is to concentrate the dilute gaseous hydrocarbons in the purged exhaust gas through a concentration adsorption tower (adapter) and remove it from this concentrated adsorption tower (adapter).
  • the gas is discharged in a state where gaseous hydrocarbons in the purged exhaust gas have been concentrated by applying a displacement purging means to the desorption tower in advance.
  • a method for cooling and liquefying the purged exhaust gas is one of the solutions.
  • any of the above-mentioned means liquefaction of gaseous hydrocarbons in the purged exhaust gas is possible only by cooling the purged exhaust gas, but involves means for concentrating the gaseous hydrocarbons in the purged exhaust gas, Moreover, it can be said that the enrichment means itself is complicated.
  • any of the above-mentioned means is not easily cooled and requires a powerful refrigerator, so that it is complicated to concentrate lean gaseous hydrocarbons. It is.
  • Oite activated carbon adsorption method has been widely used conventionally, when processing a large amount of gas that per minute hundred m 3, are used primarily fibrous active carbon
  • K-filter trade name, manufactured by Nitto Bo
  • Pyromex trade name, manufactured by Toho Rayon Co., Ltd.
  • a feature of this method is that it has a sorbent layer so that it can process large quantities of gas. However, it is difficult to reduce the hydrocarbon concentration in the gas discharged into the atmosphere to "100 ppm or less".
  • switching between adsorption and desorption is controlled by a time control via a solenoid valve.
  • time control it is necessary to know in advance the time required for the adsorption tower to break through experiments and experiences.
  • the concentration at the time of breakthrough is a trace concentration of several 10 ppm or less according to the recent severe air pollution control law, and the concentration that requires detection before that is 1-2 ppm.
  • the order is as follows, and requires a very dog-based and precise measuring device.
  • Adsorption, using a twin tower PSA purifier desorption performs adsorption wet gas in a state where pressurized adsorption tower 5 ⁇ 1 O kg Z cm 2 without using a vacuum pump, dry from the top
  • the gas flow rate through the adsorption tower that changes every moment, the inlet and outlet of the adsorption tower
  • the microcomputer stores the operating conditions of each part, including temperature, inlet and outlet pressures of the adsorption tower, and regeneration pressure of the desorption tower, as data, and calculates the material balance and heat balance instantaneously.
  • a method that controls the desorption time and indirectly automatically controls the timing of switching between adsorption and desorption. Is disclosed.
  • the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 55-35996 is a method in which switching between adsorption and desorption is performed not by time control but by a microcomputer in which the operating state of the device is stored. It was an epoch-making proposal in that it was left to the public, but at the time, there was no superior adsorption model as at present, so the simulation method could not be used. That is, the idea of “predicting the breakthrough concentration by simulation of an adsorption model” was not reached.
  • the concentration of the adsorbed component in the gas is quickly detected from the measurement port embedded in the adsorbent layer, and the solenoid valve is automatically switched when the concentration reaches a certain level. Proposed.
  • the adsorbent has a pore size of 10 OA from 5 people, such as granular activated carbon or silica gel, the concentration and temperature fluctuate locally. There is no guarantee that it will rise toward the exit with a uniform width without deviation. Therefore, it is difficult to specify the position to be measured. If the measurement port is inserted too deep from the top, it is hard to say that it is better than time control. For this reason, at present, the mainstream technology for switching between absorption and desorption is simple time control.
  • the present invention has been made in view of the problems and disadvantages of the prior art described in the above section ⁇ Prior art related to waste gas treatment method> and ⁇ Prior art related to absorption / desorption switching means>. This is an attempt to further improve the prior art.
  • the present invention concentrates the dilute gaseous hydrocarbons contained in a large amount of waste gas, extracts it as an extremely small amount of gas as a whole, and incurs an economic burden in incineration, industrial waste treatment, or liquefaction.
  • the objective (technical issue) is to reduce significantly.
  • the present invention also provides a method and an apparatus for detoxifying a large amount of waste gas containing a dilute gaseous hydrocarbon, wherein the waste gas is treated using a solid adsorbent such as hydrophobic silica gel, activated carbon, or synthetic zeolite. Safe, easy and efficient separation of harmful hydrocarbons from gas, and residual gas in waste gas released into the atmosphere after treatment
  • An object of the present invention is to provide a "method for treating a lean gaseous hydrocarbon contained in waste gas and an apparatus for performing the method", which can make the concentration of gaseous hydrocarbon less than 100 ppm.
  • Still another object of the present invention is to provide a method and apparatus which can be made portable so that the system can be integrated and mounted on a skid when the above method is implemented as an apparatus. Disclosure of the invention
  • the method according to the present invention (the method for treating a lean gaseous hydrocarbon contained in waste gas) is as follows:
  • the waste gas containing gaseous hydrocarbons is passed through one of the adsorbers, the gaseous hydrocarbons are adsorbed by the adsorbent layer in the adsorber, and the waste gas containing substantially no gaseous hydrocarbons is discharged into the atmosphere. Release to
  • the other adsorber is switched to desorption, and the gaseous hydrocarbon adsorbed on the adsorbent layer in the adsorber is desorbed by suction with a vacuum pump, and is converted into waste gas, which is transferred to purged exhaust gas.
  • the method according to the present invention comprises:
  • the adsorbent layer is composed of a layer of activated carbon and Z or hydrophobic silica gel, and a synthetic zeolite layer is disposed on top of the layer.
  • the temperature in the adsorbent layer can be easily and promptly kept constant at around room temperature, and the performance of the adsorbent can be fully exhibited without waste.
  • a gaseous hydrocarbon is pre-coated on the adsorbent or the adsorbent layer filled in the adsorption device
  • Air or liquid "water” heated above the boiling point of the hydrocarbon to be adsorbed is used as a means for releasing gaseous hydrocarbons adsorbed on the adsorbent layer in the adsorption device. .
  • an adsorbent other than activated carbon is used.
  • air having a high temperature of up to 250 ° C can be used as a purge gas.
  • this water is vaporized inside the desorption device in combination with the vacuum pump, and works in the same manner as the purge gas.
  • the amount of vaporized gas has the remarkable effect of being able to be purged with a gas amount as small as "several tenths" when using conventional steam.
  • the “means for switching to desorption before the adsorbent layer breaks through” that is the second feature of the present invention includes:
  • a temperature detection port is provided at the top of the adsorbent layer, and the solenoid valve is automatically switched when the temperature from the temperature detection port stops rising.
  • the hydrocarbon concentration in the clean gas discharged from the adsorption device into the atmosphere can be reduced to 100 ppm or less.
  • the "adsorption device having an adsorbent layer" in the device is composed of a component including an adsorbent layer, and the component is composed of a container that can be sealed but cannot be closed, that is, a container for containing the adsorbent. Regardless of the shape, the filled adsorbent does not leak from the container, and the container is provided with a large number of fine holes through which gas can flow in and out.
  • Container
  • the “adsorption device having an adsorbent layer” is an adsorption device that surrounds the adsorbent layer and has multiple built-in cylinders through which waste gas can be passed in the circumferential direction.
  • the enclosure of the adsorbent layer is a box-type component or a honeycomb-type component, and an adsorber that incorporates the component in a multiplex manner.
  • the adsorbent layer is a layer filled with fine adsorbent having a diameter of 0.1 to 1 mm,
  • FIG. 1 is a flow sheet diagram for explaining “a method for treating a lean gaseous hydrocarbon in a waste gas” which is one embodiment of the present invention.
  • FIG. 2 is a diagram showing an example of a “control panel for grasping and controlling an operating condition” in the flow sheet shown in FIG.
  • FIG. 3 is a longitudinal sectional view of an adsorption tower used in Example 1 of the present invention.
  • FIG. 4 is a longitudinal sectional view of the adsorption tower used in Embodiment 2 of the present invention.
  • FIG. 5 is a diagram further illustrating the adsorption tower of FIG. 4, wherein FIG. 5 (A) is a sectional view taken along line AA of FIG. 4, and FIG. 5 (B) is a diagram of FIG. It is the elements on larger scale of the figure.
  • FIG. 6 is a diagram showing a “water adsorption isotherm of activated carbon”.
  • 3-2b is a Y-type synthetic zeolite
  • 4a and 4b are inner cylinders
  • 5 is cooling water
  • 10 is a waste gas generation source
  • 11 is a waste gas air pipe
  • 12 is a discharge pipe
  • 13 is a discharge pipe.
  • Water pipe, 14 is a water ring vacuum pump, 15 is a purge exhaust gas pipe, 16 is a gas-liquid separator, 17 is an industrial waste treatment device, 18 is a return gas air pipe, 20 is a control Board, 21 is memory, 22 is CPU (calculation), 23 is memory (adsorption model), 41a (41b) is adsorption tower, 42a (42b), 42a ' (4 2 b ') is the outer cylinder, 4 3 a (4 3 b) is the adsorbent layer, 4 3-1 a (43 -lb) is crushed activated carbon, and 4 3 -2 a (43-2b) is Y-type synthetic zeolite.
  • BEST MODE FOR CARRYING OUT THE INVENTION hereinafter, embodiments of a method and an apparatus according to the present invention (hereinafter, simply referred to as “the present invention”) will be described, and the present invention will be described in more detail.
  • the first feature of the present invention lies in "returning all or most of the purged exhaust gas to the waste gas to be treated and increasing the hydrocarbon concentration in the adsorbent layer". Is to switch to desorption before the adsorbent layer breaks through, thereby safely, easily and efficiently treating hydrocarbons from waste gas, and after treatment, to the atmosphere.
  • the residual hydrocarbon concentration in the released gas can be less than 100 ppm, especially "less than 20 ppm".
  • the entire amount of the purged exhaust gas is returned to the waste gas to be treated, but the hydrocarbon concentration in the purge exhaust gas is reduced.
  • the adsorbent layer will break through in a very short time, which will adversely affect the treatment of waste gas. Therefore, as another embodiment of the present invention, when the hydrocarbon concentration is extremely high, a part of the purged exhaust gas is taken out, detoxified, for example, subjected to a combustion process, and the remaining (most) It is desirable to return the purge exhaust gas to the waste gas to be treated.
  • the liquid hydrocarbons can be separated and burned, or detoxified as industrial waste.
  • the breakthrough detecting means of the present invention basically includes a device. Although it is based on a built-in circuit chip, it uses an ultra-small chip, which has recently made remarkable progress, so that the above-mentioned known technology (the technology disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 55-35996) is used. It does not require a large microphone processor for the purpose of calculation as described in (1).
  • the adsorption model is entered into R ⁇ M, while By reading the operation data that changes during the operation as a logger signal into a computer and simulating it, the breakthrough concentration is preferably reduced.
  • This is completely different from the prior art in that it attempts to control the adsorption system by predicting in seconds. In other words, this is clearly different from the idea of “predicting breakthrough concentration by simulation of an adsorption model” which is a preferred embodiment of the present invention.
  • adsorption model By the way, various types of “adsorption model” have been proposed. Among them, the physical properties of the adsorbent, that is, “adsorption isotherm and adsorption pressure inside adsorption tower, vacuum degree of vacuum pump, gas flow rate in tower” , The height of the adsorbent layer and the purge coefficient are fixed, and the variable “inlet gas flow rate and concentration” is used as the switching time or the outlet of the adsorbent layer.
  • concentration breakthrough concentration
  • the second feature of the present invention that is, "switching to desorption before the adsorption device breaks through” is an essential component, because the first feature of the present invention, “purge exhaust gas” Is returned to the waste gas to be treated to increase the hydrocarbon concentration in the adsorbent layer. "
  • the present invention does not eliminate the switching means based on time control that has been performed conventionally. If the concentration of gaseous hydrocarbons contained in the gas at the inlet of the adsorption tower (waste gas / the above-mentioned uncondensed page exhaust gas) is almost constant over time, the operation of the adsorption tower is started and the destruction occurs. This is because it is one of the expedients to determine the time until the time is spent in advance, and to switch using this time as a guide in the next suction operation. You. In addition, in the adsorption apparatus developed by the present inventors, it is one of the options to adopt a “switching means by time control” by predicting the time when desorption is completed from the operation of the desorption tower. is there.
  • the means for switching the desorption tower to the adsorption tower can be time-controlled. If this means is described in detail, the operation shifts to the desorption operation, the vacuum pump starts operating, and after detecting the point when a predetermined degree of vacuum is reached, purge gas is introduced into the desorption tower, and this introduction time is set in advance. This is a method that automatically switches to the suction operation when the time is up.
  • the concentration of the gaseous hydrocarbon adsorbed on the adsorbent layer is automatically reduced to just before the breakthrough. It can be concentrated to a high concentration.
  • this purge exhaust gas can be taken out and subjected to, for example, a combustion treatment, and gaseous hydrocarbons in the purge exhaust gas can be removed. It can be separated as liquid hydrocarbons and burned, or detoxified as industrial waste.
  • the disadvantage is that if the time required for adsorption and the time required for desorption are too different, for example, it takes several days before adsorption and just before breakthrough, If the desorption process takes only a few hours, it is not necessarily the preferred method from the perspective of the person managing the work.
  • the amount of gaseous hydrocarbons to be adsorbed is extremely small near the top of the adsorbent layer, which is generated.
  • the amount of heat absorbed is extremely reduced, and more heat is radiated outside from the cooling water and the wall of the adsorption tower.
  • the signal from the measurement port inserted near the top to capture data into the chip, ie, the indicated temperature, stops, and the temperature gradually decreases over time. If the means for automatically switching the intake / desorption switching valve (solenoid valve) at this time is used together, the above-mentioned disadvantages can be solved, and this is also included in the present invention.
  • Adsorbent means that the adsorption pore diameter is controlled to a certain size, Adsorbents that are unlikely to cause unevenness in the amount of adsorption and that do not easily adsorb moisture even in areas where the relative humidity in the waste gas is as high as about 50% or more.For example, an adsorbent such as synthetic zeolite is optimal. .
  • a synthetic zeolite layer is provided on the top of the adsorbent layer, and a temperature detection port is provided in the adsorbent layer made of the synthetic zeolite.
  • a temperature detection port is provided in the adsorbent layer made of the synthetic zeolite.
  • means for automatically switching the solenoid valve when the temperature from the temperature detection port stops increasing its temperature is adopted.
  • pre-coated activated carbon or similarly pre-coated hydrophobic silica gel is preferable.
  • precoat which is a preferred embodiment of the present invention.
  • the degree to which gaseous hydrocarbons are concentrated in the adsorbent layer is, theoretically, "760725" if only hydrocarbons are adsorbed when the degree of vacuum is 25 mm Hg, That is, the density is about 25 times higher, but usually a large amount of air coexists, and the molecular diameter of nitrogen gas or oxygen gas in this air is larger than that of hydrocarbons. Therefore, nitrogen gas and oxygen gas are adsorbed in preference to hydrocarbon gas. As a result, it is empirically known that it can only be concentrated to four times the concentration of hydrocarbons at the inlet.
  • the solid adsorbent such as activated carbon, synthetic zeolite, and hydrophobic silica gel used in the present invention is not an adsorbent that does not adsorb moisture at all, but as shown in FIG. The water absorption varies greatly depending on the target concentration.
  • Fig. 6 shows the water adsorption isotherm of activated carbon, but the same can be said for other hydrophobic adsorbents.
  • the adsorbent layer is pre-coated by dripping liquid hydrocarbons into the waste gas to be treated, specifically, by spraying the liquid hydrocarbons into the conduit of the waste gas to be treated. can do.
  • the pre-coating agent in addition to the above liquid hydrocarbons, for example, substances such as hydrocarbons having an affinity for water and having a higher boiling point than water can be used.
  • the present inventor developed a system for processing a large amount of waste gas containing gaseous hydrocarbons, using the elemental technology on the hard surface called “loga signal”, which is a means for capturing data, in this system.
  • a new technique on the so-called soft surface that is, a “simulation of a ROMized adsorption model” that has been cleverly incorporated into the control system, it is possible to shorten the time regardless of the change of the hydrocarbon concentration at the inlet.
  • the temperature in the adsorbent layer was easily and promptly kept constant at around room temperature.
  • the timing of switching from adsorption to desorption is not simply set by a cycle of time, but is left to the discretion of a personal computer (software) that incorporates an "adsorption model", thereby reducing the performance of the adsorbent without waste. It is now possible to make full use of it. For this reason, it became possible to concentrate the lean hydrocarbons in the purge exhaust gas to just before breakthrough, and to extract it as an extremely rich hydrocarbon with a very small amount of purge exhaust gas.
  • any solid adsorbent having an affinity for the hydrocarbon gas in the waste gas can be used regardless of whether the material is flammable or nonflammable.
  • hydrophobic silica gel which is inexpensive and easy to handle is desirable. The reason is no. —Because the temperature of the digas can be raised to about 250 ° C for use.
  • non-combustible silica gel When using non-combustible silica gel, if it is hydrophobized with a silane coupling agent such as trimethylchlorosilane or treated at high temperature for a long time, it will be hydrophobic and lipophilic.
  • adsorbents or adsorbents precoated with high boiling hydrocarbons such as ethylene glycol heptane. But the best adsorbent is
  • solid adsorbents such as activated carbon, synthetic zeolite, silica gel, and activated alumina used as adsorbents have strong affinity for gaseous hydrocarbons, but are also widely used as heat insulators.
  • the other adsorbents have a wide distribution of adsorption pore diameters, so that the concentration at the adsorption site is not uniform and mouth-to-mouth heating tends to occur.
  • the recommended way to avoid this is to place the synthetic zeolite at the top of the adsorbent layer, ie, near the outlet.
  • Synthetic zeolite unlike hydrophobic silica gel or granular activated carbon, has a strictly controlled pore size to a certain size. Depending on the material selected, some varieties cover almost the entire molecular diameter of gaseous hydrocarbons. is there. In addition, despite the fact that the ratio of adsorbing gaseous hydrocarbons is 15% to 20% by weight, the amount of water adsorbed is 10% even for gases with RH of 50% or more. % Or less. For this reason, there is no deviation in the adsorption band having a certain width moving in this layer.
  • the port for detecting the concentration and temperature to be taken in as a data logger signal must be located at the center of the synthetic zeolite layer. In this way, the breakthrough point is detected.
  • the point at which the temperature indication at the central portion stops the temperature rise due to the heat of adsorption can be used as a guide for switching.
  • Such synthetic Zeorai DOO the ratio of S i 0 2, A 1 2 0 3 is 2 0 or more, those having a pore size of about 8 angstroms Ichimu is desirable.
  • the heat of adsorption generated in the adsorbent layer is used.
  • an adsorbent layer for adsorbing gaseous hydrocarbons and a cooling water layer for cooling the adsorbent layer are adjacent to each other. It is preferable to use a “double cylinder or multiple cylinder type adsorption tower” configured. In consideration of the tendency of static electricity generated in the adsorbent layer to gather at the center of the layer, use of an adsorption tower with a structure in which a metal cylinder is arranged at the center to release static electricity while also cooling. Is desirable.
  • the adsorption tower 1a (1b) comprises an outer cylinder 2a (2b) and an adsorbent. Layer 3 a (3 b), inner cylinder 4 a (4 b), and cooling water 5.
  • the adsorption tower 1a (1b) is an adsorption tower used in Example 1 of the present invention described later, and 3-la (3-lb) in the figure is activated carbon, and 3-2a ( 3-2b) is a Y-type synthetic zeolite.
  • the adsorption tower 1a (1b) of the present invention is that if the pressure inside the adsorption tower is increased, the effective adsorption amount of hydrocarbons adsorbed by the adsorbent is remarkably increased. since the pressure is a matter of course to say from the theory of PSA process, even in the practice of the present invention, the gauge pressure "1 kg / cm 2 or less that does not conflict with the internal pressure of the adsorption tower la (lb) to the" high pressure regulations " Working with "is highly desirable.
  • a conventionally used “tower-type, adsorption device that is densely packed with an adsorbent” can also be used, but when the amount of waste gas to be treated is large, In this case, a problem arises with this conventional type.
  • adsorption efficiency is closely related to the size of the adsorbent particles. For example, when comparing the case where a large particle size adsorbent and a small particle size adsorbent are packed in an adsorbent layer of the same capacity, it is natural that the smaller the particle size, the higher the efficiency, but the higher the flow rate. There is a problem even if it is too small. For this reason, the diameter of the conventionally used adsorbent depends on the type and shape of the adsorbent, but 2-3 mm is appropriate.
  • the adsorber which avoids the flow of the adsorbent and is densely packed, has a structure in which the cross of fibrous activated carbon is coordinated inside the adsorber and the waste gas flows in the direction across the cloth.
  • K-filter trade name, manufactured by Toyobo
  • Pyromex trade name, manufactured by Toho Rayon Co., Ltd.
  • the adsorber with the above structure has the advantage that a large gas passage area can be obtained, but has the disadvantage that the adsorbent layer is thin, so that the contact time is short and dilute hydrocarbons in waste gas cannot be collected sufficiently. are doing.
  • the desorption means of this device cannot be considered other than the use of steam, and cannot be used together with a vacuum pump.
  • the adsorption efficiency is "Kfav", that is, "overall mass transfer capacity”
  • Kfav the adsorption efficiency
  • the value of the coefficient (1 / sec) is shown in the following table. From the experiments conducted by the present inventor and the analysis of the operation results with the industrial equipment constructed by the present inventor, the value of K fav When the adsorbent is used, it is almost in the range of "3 to 6", depending on the properties of the gaseous hydrocarbon.
  • the adsorption performance is several times better in the range of "15 to 25". Specifically, the contact time between the gas and the adsorbent is "about 1 Z5".
  • an adsorption device having an adsorbent layer is composed of a component including an adsorbent layer, and the component can be hermetically sealed. It consists of a container that cannot be closed, that is, regardless of the shape of the container containing the adsorbent, the filled (contained) adsorbent does not leak out of the container, and It is a container that has a configuration with many micropores that allow gas inflow and outflow.
  • the adsorbing device having an adsorbent layer is an adsorbing device that surrounds the adsorbent layer and has multiple built-in cylinders through which the waste gas can be passed in the circumferential direction;
  • the enclosure of the adsorbent layer is a box-type component or a honeycomb-type component, and is an adsorption device in which the component is multiplexed;
  • fine particles of 0.1 to 1 mm are used, thereby shortening the contact time with the gas,
  • the configuration of the adsorbent layer in the adsorber is multiplexed to increase the gas passage area.
  • the use of fine particles of 0.1 to 1 mm as the adsorbent has an excellent effect that the contact time can be reduced to "about 1/5" as compared with the conventional means. And to say that it can be reduced to "about 1 Z5" This means that the thickness of the adsorbent layer will also be “about 1 Z5".
  • the thickness (layer height) is “l to 2 m”.
  • the thickness of the adsorbent layer is “about 1 Z5”. From that point, the thickness is "20 cm to 40 cm", and as a result, there is an excellent effect that the adsorbent layer does not need to be cooled in principle.
  • the concentration of the adsorbed hydrocarbon is extremely low because the waste gas ends up in one pass through this adsorbent layer, and the means for desorption is other than steam. I could not imagine.
  • the hydrocarbon concentration in the adsorbent layer can be increased. This makes it possible to use a vacuum pump that could not be achieved by using a vacuum pump.
  • the adsorption tower 41a (41b) is filled with the adsorbent layer 43a (43b).
  • the outer cylinder is composed of a double cylinder of 42a (42b) and 42a '(42b'). Then, the waste gas passes through the adsorbent layer 43a (43b) as shown by the arrow line in Fig. 5 (B), thus increasing the gas passage area. It is.
  • This adsorption tower 4 la (41b) is an adsorption tower used in Example 2 of the present invention described later, and 43-1a (43 -lb) in the figure indicates crushed activated carbon, 43 -2a (43-2b) is a Y-type synthetic zeolite.
  • the adapter-type system disclosed in Japanese Patent Nos. 2,840,563, 2,766,793, and 2,382,335, which have already been obtained by the present inventors instead of using the purging method and the purging method, the gaseous hydrocarbons in the purged exhaust gas are recovered without using a method of washing with the same type of hydrocarbon liquid, and the desorbed gas is recycled. Instead of using a complicated cooling means to recover gaseous hydrocarbons from the gas as a liquid after enriching the hydrocarbon concentration in the adsorption tower, a simple and economical method in which the recovery means is omitted is provided. Provided.
  • air or water heated above the boiling point of the hydrocarbon to be adsorbed can be used as a means for releasing gaseous hydrocarbons adsorbed on the adsorbent layer.
  • water is particularly preferred (see below).
  • the means for detoxifying dilute hydrocarbons contained in a large amount of waste gas the adsorption method has been used exclusively.
  • the adsorbent used is, with exceptions, granular activated carbon or fibrous activated carbon.
  • This type of activated carbon has excellent adsorption capacity compared to other adsorbents, but has the drawback that it is extremely difficult to desorb. For this reason, at the time of desorption as described above, at present, a large amount of steam, which is about three times the amount of filled activated carbon, is used.
  • the hydrocarbons entrained in the steam are detoxified together with water by wastewater treatment means such as activated sludge treatment equipment.
  • the gaseous hydrocarbon desorbed along with the heated purge gas is a gas suitable for burning as it is as a purge exhaust gas.
  • the degree of vacuum to be sucked is "60 to 15 OT orr". Since the vacuum pump is expensive, it can be said that this is a remarkable effect of the application of the present invention.
  • the desorption tower By injecting water into the desorption tower, not only can it be vaporized inside the desorption tower with the help of a vacuum pump and exert the same effect as the purge gas, but also the amount of vaporized gas can be reduced by the conventional steam use. In this case, the gas can be purged with a small gas amount of "several tenths".
  • a water-sealed vacuum pump is preferable as the vacuum pump used at that time.
  • the reason is that the concentrated hydrocarbon gas is mixed with the water in the water seal to obtain wastewater and wastewater suitable for industrial waste treatment.
  • the embodiment according to the present invention is as described in detail above.
  • the method according to the present invention can employ a publicly known PSA method or PTSA method.
  • VSA method, VTSA method, etc. are also included in the present invention.
  • the present invention provides a treatment method for concentrating and separating a dilute gaseous hydrocarbon contained in a waste gas and an apparatus for performing the method, wherein a dilute hydrocarbon generated at the time of coating is provided.
  • a dilute hydrocarbon generated at the time of coating is provided.
  • multi-component hydrocarbon gas but also benzene, toluene, It is widely applied to dilute single-component gases such as trichloroethylene, methylethylketone, and even freon.
  • FIG. 1 is a flow sheet diagram for explaining “a method for treating a lean gaseous hydrocarbon in a waste gas” which is one embodiment of the present invention.
  • FIG. 2 is a flow sheet diagram shown in FIG. It is a figure which shows an example of the "control panel for grasping and controlling an operating condition" in a flow sheet.
  • FIG. 3 is a longitudinal sectional view showing one example (Example 1) of the structure of the adsorption tower used in the flow sheet shown in FIG.
  • the adsorption column la (lb) composed of the double cylinder of b) was used.
  • the cooling water 5 flowing through the inner cylinder 4a (4b) is turbulent so that it flows countercurrently to the waste gas flowing through the adsorbent layer 3a (3b).
  • granular activated carbon granular Shirasagi No .: trade name, manufactured by Takeda Pharmaceutical Co., Ltd.
  • Y-type synthetic zeolite 360 HUD: trade name, manufactured by Tosoh Corporation
  • Fig. 3 the Y-type synthetic zeolite 3-2a (3-2b) was filled in the upper part of the granular activated carbon 3-la (3-lb) into the adsorption tower 1a (1b), This was used as an adsorbent layer 3a (3b).
  • the granular activated carbon used was pre-coated with benzene vapor in advance.
  • Example 1 will be described in detail with reference to FIG. 1.
  • a waste gas generated from a waste gas generation source (a waste gas containing about 500 ppm benzene: 20 liters) (Amount of gas in Torr Z) is blown to the adsorption tower 1a by a blower (not shown) that compresses the gauge pressure to 1 kg / cm or less or the waste gas air pipe 11 by its own pressure.
  • the gas velocity passing through the adsorbent layer 3a (3b) was "about 10 cm / sec".
  • the treated waste gas after the adsorption process contains 20 ppm or less of benzene vapor from the top of the adsorption tower la (adsorption tower 1b after switching to the desorption step) via the discharge pipe 12. Released into the atmosphere as air (clean gas).
  • the adsorption towers 1a and 1b are operated while alternately switching between the above adsorption step and the desorption step described later, but at this switching point, the adsorbent layer in the adsorption towers 1a and 1 lb is broken. This is done before passing through, and by automatically opening and closing valves (2) and (2) shown in Fig. 1.
  • valves (e) and (e) for switching between suction and desorption are opened and closed
  • the water ring vacuum pump 14 is operated at about 60 T 0 rr, and the pressure in the adsorption tower 1 a (the tower switched to desorption) is reduced to a low pressure (vacuum).
  • the supplied water turns into steam in the adsorption tower 1a to become a purge gas.
  • the gas is extracted as purged exhaust gas from the purge gas air supply pipe 15 through the water ring vacuum pump 14.
  • Room temperature industrial water was used to cool the purged exhaust gas sucked by the water ring vacuum pump 14. That is, the purge exhaust gas is sent to the gas-liquid separator 16.
  • the gas-liquid separator 16 is cooled by industrial water flowing through a cooling pipe (not shown) arranged inside.
  • the benzene vapor in the purged exhaust gas is condensed and liquefied in the water-sealed water in the gas-liquid separator 16 connected to the lower part, and is separated from uncondensed gas. Accumulated water And benzene are taken out of the system and are subjected to industrial waste treatment with an industrial waste treatment unit 17.
  • the benzene vapor remains in the exhaust gas not condensed in the gas-liquid separator 16
  • the benzene vapor is returned to the waste gas air pipe 11 again via the return gas air pipe 18, and is returned together with the waste gas. To perform the adsorption process.
  • the uncondensed gas contains a high concentration of residual benzene, and by returning the entire amount to the waste gas supply pipe 11, the benzene concentration in the adsorption tower is further increased. Then, by using the above-described means, the switching time of the valve (e) is set by predicting the time at which the adsorbent layer in the adsorption tower breaks through, and the operation is automatically switched to the desorption operation.
  • a to J shown in Fig. 1 indicate the positions of the instruments provided to grasp the operation status.
  • (a) to (2) indicate the This shows the position of the provided valve.
  • FIG. 2 shows a control panel 20 for grasping and controlling the operation status in the flow shown in FIG. 1, and includes a memory 21, a memory (adsorption model) 23, and a CPU ( Arithmetic) 22.
  • a memory adsorption model
  • CPU Arithmetic
  • the concentration When the concentration is low, the concentration can be concentrated several times in the adsorption tower, and by devising cooling means to remove the heat generated in the adsorbent layer (see Fig. 3 above), local heating is avoided.
  • the temperature of the adsorbent layer during the operation period was almost room temperature.
  • the benzene concentration in the gas released into the atmosphere from the discharge pipe 12 was substantially less than 20 ppm.
  • FIG. 4 is a longitudinal sectional view of an adsorption tower used in Example 2.
  • FIG. 5 is a diagram further explaining the adsorption tower of FIG. 4, wherein FIG. 5 (A) is a cross-sectional view taken along the line A-A of FIG. 4, and FIG. 5 (B) is a diagram of FIG. It is the elements on larger scale of the figure.
  • the adsorbent layer Adsorption tower 4 1a (4 1 b) consisting of a double cylinder of outer cylinder 4 2 b (4 2 b) and 4 2 a '(4 2 b') filled with 4 3 a (4 3 b) ) was used.
  • crushed activated carbon with a particle size of 0.4 mm (HC42: trade name of Tsurumi Coal) and Y-type synthetic zeolite with a particle size of 1.0 mm (360 HUD: East (Trade name, manufactured by Soviet Union).
  • the Y-type synthetic zeolite 43-2a (43-2b) is adsorbed on the top of the broken activated carbon 43-la (43-lb).
  • the column 41a (41b) was packed and used as an adsorbent layer 43a (43b).
  • the crushed activated carbon used was previously pre-coated with benzene vapor.
  • Example 2 the above-mentioned crushed activated carbon and Y-type synthetic zeolite were used using the adsorption towers 41a (41b) shown in FIGS. 4 and 5 (A) and (B) described above. Except for the above, waste gas (waste gas containing about 50,000 ppm of benzene: gas amount of 300 liters Z) was treated under the same conditions and means as in Example 1. At this time, the gas velocity passing in the circumferential direction through the adsorbent layer 43a (43b) was "1.5 cmZ seconds".
  • Example 2 the benzene concentration in the gas released into the atmosphere from the discharge pipe 12 (see Fig. 1) was such that it could not be detected with a commercially available HC concentration detection pipe (isobutane conversion). It was a trace amount.
  • Example 1 the benzene concentration in the gas released into the atmosphere is 20 ppm or less, whereas in Example 2, as described above, a trace amount It can be understood that the amount is superior to that of Example 1.
  • the double-cylinder adsorption towers 1a and 1b shown in FIG. 3 are used as the first embodiment of the present invention.
  • the present invention is not limited to such a double cylinder.
  • the suction of the multiple cylinders shown in FIGS. Although a landing tower was used, the present invention is not limited to such a multi-cylinder, and for example, an adsorbent configured by filling an adsorbent into a honeycomb-shaped core and bundling the same, or It is also possible to use an adsorption device or the like constituted by packing adsorbents in a box and stacking them.
  • the benzene concentration specified in the amendment of the Air Pollution Control Law not only can the emission standard “30 ppm or less” be completely cleared, but even if this figure becomes less than half strict, it can sufficiently cope with it.
  • the present invention can be configured to be portable so that the system can be integrated and mounted on a skid when the method according to the present invention is implemented as an apparatus.

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Abstract

La présente invention concerne un dispositif et un procédé de traitement de gaz permettant d'une part de traiter une grande quantité de gaz de combustion contenant du carbure d'hydrogène gazeux liquide en vue de séparer le carbure d'hydrogène gazeux dilué de manière facile, sûre et efficace, et d'autre part de réduire, après le traitement, la concentration de carbure d'hydrogène gazeux restant dans le gaz de combustion devant s'échapper dans l'air jusqu'à 100 ppm. Ce procédé consiste à: (1) utiliser comme dispositif d'adsorption une couche d'adsorption et des colonnes d'adsorption (1a, 1b) pour refroidir cette couche, (2) remplir les colonnes d'adsorption de charbon actif et verser dessus un zéolite synthétique de type Y, (3) basculer en alternance entre adsorption et absorption selon un temps de basculement déterminé par la commande automatique de valves de basculement adsorption/absorption (d), en fonction d'une instruction de 'concentration estimée à laquelle la couche d'adsorption se rompt' provenant d'un enregistreur de données, (4) utiliser de 'l'eau' lors de l'adsorption et l'aspirer par une pompe à vide étanche à l'eau (14), et enfin, (5) retourner la quantité totale de gaz de combustion purgé dans un tuyau d'alimentation de gaz d'échappement (11), tout en (6) traitant le liquide provenant d'un séparateur de liquide/gaz (16) dans un dispositif (17) de traitement de déchets industriels.
PCT/JP2000/000513 1999-02-17 2000-01-31 Dispositif et procede de traitement de carbure d'hydrogene gazeux dilue contenu dans un gaz de combustion WO2000048713A1 (fr)

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AU23233/00A AU2323300A (en) 1999-02-17 2000-01-31 Method for treating dilute gaseous hydrogen carbide contained in waste gas and device for performing the method
KR1020017010446A KR20010114209A (ko) 1999-02-17 2000-01-31 폐기 가스 중에 포함되는 희박한 가스상태 탄화 수소의처리방법 및 이 방법을 실시하기 위한 장치

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JP11077495A JP3133988B2 (ja) 1999-02-17 1999-03-23 廃棄ガス中に含まれる希薄なガス状炭化水素の処理装置

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CN104190205A (zh) * 2014-09-26 2014-12-10 江南大学 一种废气回收循环工作方法和装置
CN106039921A (zh) * 2016-06-30 2016-10-26 清本环保工程(杭州)有限公司 一种有机废气处理方法
CN114887448A (zh) * 2022-04-29 2022-08-12 上海至纯系统集成有限公司 一种干式吸附尾气处理器

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JP4786043B2 (ja) * 2001-03-09 2011-10-05 三菱重工環境・化学エンジニアリング株式会社 固定層式活性炭吸着塔
JP4418313B2 (ja) * 2004-07-07 2010-02-17 富士シリシア化学株式会社 充填層型熱交換型吸着装置及び該吸着装置を用いた所定吸着質濃度のガスを得る方法
KR100770180B1 (ko) * 2006-05-19 2007-10-25 주식회사 포스코 소결 배가스 흡착탑 제어장치
DE102006032609A1 (de) * 2006-07-11 2008-01-17 Zeosys Gmbh Verfahren zur Rückgewinnung halogenierter Kohlenwasserstoffe
JP5701063B2 (ja) * 2008-01-02 2015-04-15 ツェオシス ゲゼルシャフト ミット ベシュレンクテル ハフツングＺｅｏＳｙｓ ＧｍｂＨ ハロゲン化炭化水素の回収方法
CN107290205B (zh) * 2016-04-11 2020-05-15 中国石油化工股份有限公司 用于解析热稀烃的装置
CN113577982B (zh) * 2021-08-18 2022-05-31 如东深水环境科技有限公司 智能废气处理装置

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WO1997020618A1 (fr) * 1995-12-06 1997-06-12 Cosmo Engineering Co., Ltd. Procede pour traiter ou recuperer des hydrocarbures gazeux contenus dans des gaz de rejet
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CN104190205A (zh) * 2014-09-26 2014-12-10 江南大学 一种废气回收循环工作方法和装置
CN106039921A (zh) * 2016-06-30 2016-10-26 清本环保工程(杭州)有限公司 一种有机废气处理方法
CN114887448A (zh) * 2022-04-29 2022-08-12 上海至纯系统集成有限公司 一种干式吸附尾气处理器

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