JP2001293333A - Device and method for treating organic chlorinated compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make dioxins harmless, while adsorbents are used repeatedly, thereby reliably preventing the dioxins from being regenerated and to eliminate the risk of inflammation or explosion of the adsorbents. SOLUTION: An adsorption layer, on which zeolite is carried as an adsorbent, is provided in a treating device 20 for gas. An object gas, which may contain dioxins and precursors whereof, is introduced into the device 20. The dioxins and the precursors thereof in the object gas are adsorbed on the zeolite. A hot nitrogen gas is introduced into the device 20 to make harmless the dioxins and precursors thereof adsorbed on the zeolite by dechlorinating the dioxins and precursors by means of the hot nitrogen gas, thereby removing the dioxins and precursors from the zeolite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to dioxins and dioxins contained in emissions from combustion equipment or other equipment capable of producing dioxins and their precursors, such as waste incinerators, etc. Precursor and PC
The present invention relates to an organic chlorine compound treating apparatus and an organic chlorine compound treating method for adsorbing and decomposing an organic chlorine compound such as Class B to make it harmless.

[0002]

2. Description of the Related Art Various proposals have conventionally been made as techniques for removing and detoxifying dioxins.

[0003] Among them, those which attempt to decompose dioxins by heating while using a catalyst to make them harmless,
The risk of dioxins being regenerated during cooling is relatively high, and measures have been required to prevent this.

[0004] Further, those which attempt to adsorb and remove dioxins by using an adsorbent increase the cost due to consumption of the adsorbent and require treatment of the adsorbent after use.
In particular, when activated carbon is used as an adsorbent, there is a risk that the adsorbent may ignite or a coal dust explosion may occur when treating a high-temperature object such as exhaust gas from an incinerator.

[0005] The present invention has been made in view of the above-mentioned problems in the prior art, and an object of the present invention is to repeatedly use an adsorbent to ensure the regeneration of dioxins and the like. An object of the present invention is to provide an organic chlorine compound processing apparatus and an organic chlorine compound processing method that can perform a detoxification treatment of dioxins and the like while preventing the occurrence of high toxicity, and that does not cause the risk of ignition or explosion of the adsorbent.

[0006]

(1) An apparatus for treating an organochlorine compound according to the present invention, which achieves the above object, comprises: a treatment device having an adsorbent for a target organochlorine compound comprising zeolite therein; An object supply means for supplying an object to be treated, which may contain an organic chlorine compound, to the adsorbent, and an inert and inactive substance for treatment for detoxifying and detoxifying the target organic chlorine compound adsorbed on the adsorbent. And / or a processing substance supply means for supplying a reducing processing gas to the adsorbent, wherein the processing gas reaching the adsorbent dechlorinates the target organic chlorine compound adsorbed by the adsorbent. It is characterized in that it is a processing hot gas at a temperature to be obtained.

Further, the method for treating an organic chlorine compound of the present invention comprises introducing an object to be treated that can contain the target organic chlorine compound into an adsorbent for the target organic chlorine compound made of zeolite, thereby containing the target organic chlorine compound. The target organochlorine compound adsorbed by the adsorbent is adsorbed onto the adsorbent, and an inert and / or reducing heat gas for treatment is introduced to the adsorbent as a treatment substance. It is characterized by dechlorination and detoxification.

By using the apparatus for treating an organic chlorine compound of the present invention, the method for treating an organic chlorine compound of the present invention can be carried out as follows.

[0009] By supplying an object to be treated which can contain the target organic chlorine compound to the adsorbent in the processing unit by means of the object to be treated supply means, the target organic chlorine compound which can be contained in the object to be treated is added to the adsorbent. Adsorbed.

In the state where the target organochlorine compound is thus adsorbed on the adsorbent, an inert and / or reducing processing gas (ie, an inert processing gas and a reducing processing gas) is used as the processing substance. Gas or both) is supplied to the adsorbent in the processing unit by the processing substance supply means. The processing gas that has reached the adsorbent may be adsorbed by, for example, heating before introduction into the processing unit, heating in the processing unit, heating by a reaction in the processing unit, or without such heating. The target organic chlorine compound adsorbed by the adsorbent is a processing hot gas at a required temperature that can dechlorinate the target organic chlorine compound, and the target organic chlorine compound adsorbed by the adsorbent is detoxified by the dechlorination by the processing hot gas. To desorb from the adsorbent. By detoxifying and desorbing the target organic chlorine compound in this way, the target organic chlorine compound adsorption capacity of the adsorbent is regenerated, and the adsorbent can be used repeatedly. Since dechlorination and detoxification are performed by the inert and / or reducing heat gas for treatment, regeneration of the target organic chlorine compound can be prevented with high reliability.
In addition, a part of the target organic chlorine compound adsorbed by the adsorbent may be decomposed depending on various conditions without depending on the processing hot gas.

The organic chlorine compound processing apparatus includes: a processing object source which is a supply source of a processing object which may contain a target organic chlorine compound; and a processing object supplied from the processing object source. An object introduction part for introducing and leading to the adsorbent in the processing unit, and a treated object for discharging the treated object obtained by subjecting the treated object to the adsorption treatment of the target organic chlorine compound from the processing unit to the outside Discharge part, treatment substance source that is a supply source of treatment substance to dechlorinate and detoxify the target organochlorine compound adsorbed by the adsorbent, and treat the treatment substance supplied from the treatment substance source A treatment substance introduction section for introducing the substance into the vessel and leading to the adsorbent; and a production section for discharging at least a product generated by dechlorinating the target organic chlorine compound by the treatment substance to be detoxified from the treatment apparatus. It has a material discharge section and adsorbs Treatment material while traveling to and can be assumed to be inert and / or reducing treatment for hot gas having a temperature which can be dechlorinated target organic chlorine compounds adsorbed by the adsorbent.

This organic chlorine compound treating apparatus can be used as follows.

[0013] An object to be treated, which may contain the target organochlorine compound, is introduced from the object to be treated into the processor through the object introduction section, whereby the object to be treated is guided to the adsorbent in the processor. Then, the target organic chlorine compound that can be contained in the object to be treated is adsorbed by the adsorbent. The object to be processed is subjected to the adsorption process in this way to become a processed product, and the processed product is discharged from the processed product discharge unit.

In a state where the target organic chlorine compound is adsorbed by the adsorbent, the processing substance is introduced into the processing unit from the processing substance source through the processing substance introduction section, whereby the processing substance is adsorbed. Led to. The treatment substance that has reached the adsorbent is an inert and / or reducing treatment heat gas having a temperature capable of dechlorinating the target organic chlorine compound adsorbed on the adsorbent. That is, the processing substance that has reached the adsorbent is an inert and / or reducing processing gas, and the processing gas may be heated, for example, before the introduction into the processing apparatus, or may be heated in the processing apparatus. An inert processing hot gas having a required temperature capable of dechlorinating the target organochlorine compound adsorbed on the adsorbent by heating or the like by a reaction in a treatment device or without such heating, and / or It is a reducing hot gas for processing. Therefore, the target organochlorine compound adsorbed by the adsorbent is detoxified by dechlorination with the hot gas for treatment and desorbed from the adsorbent, and at least the target organic chlorine compound is dechlorinated and detoxified by the treatment gas to be produced. The resulting product and other substances, such as, for example, process gases, are discharged from the product outlet. By detoxifying and desorbing the target organic chlorine compound in this way, the target organic chlorine compound adsorption capacity of the adsorbent is regenerated, and the adsorbent can be used repeatedly. Since dechlorination and detoxification are performed by the inert and / or reducing heat gas for treatment, regeneration of the target organic chlorine compound can be prevented with high reliability.

As the treatment device, for example, a treatment device having a gas-tightness such as a chamber, a tube, a tower and the like which does not leak an object to be treated or an adsorbent when using a granular or powdery zeolite is appropriately selected. I can do it. In addition, it is also possible to use, for example, a rotary drum or rotary kiln type, or a type using granular or powdery zeolite for the fluidized bed.

Each of the object introduction section, the processing substance introduction section, the processed material discharge section, and the product discharge section may have an opening which can be opened and closed by, for example, an on-off valve. The object introduction part, the processing substance introduction part, the processed material discharge part, and the product discharge part can be separately provided, and for example, any two of them are common (for example, the object introduction part and the processing substance discharge part). The substance introduction part, or the processed material discharge part and the product discharge part, or the processed material discharge part and the processing substance introduction part), the other two being separate, and any two are common (for example, (The substance introduction part and the treatment substance introduction part, or the processed material discharge part and the treatment substance introduction part), the other two are also common, any three are common, or all are common It can be.

In the case where the object introduction part and the treatment substance introduction part or the treated matter discharge part and / or the product discharge part are separate, they reach the treated matter discharge part from the object introduction part. The path and the path from the processing substance introduction section to the product discharge section are almost the same in the normal case.
The direction can be reversed.

The processing object supply means may include a processing object source and an object introduction unit.

Examples of the processing object supply means include a processing object source such as an incinerator or other apparatus for generating or storing the processing object, a gas processing object supply pipe, and a gas processing object supply. And a combination with a blower or a fan for feeding a solid processing target, a screw conveyor for feeding a solid processing target, and an on-off valve for the target introduction unit and the like, and a target feeding and / or distributing device.

The processing substance supply means may include a processing substance source and a processing substance introduction unit.

Examples of the processing substance supply means include a nitrogen gas generator, a nitrogen gas separator, a nitrogen gas source such as a nitrogen gas cylinder, other inert gas sources such as an inert gas cylinder, and reducing gas. A processing substance source such as a reducing gas source such as a cylinder, a supply source of a substance generating a reducing gas by thermal decomposition or vaporization (e.g., a substance that is easily volatilized such as methanol or ethanol), and a processing substance supply Combination with a processing substance supply and / or distribution device such as an on-off valve for a pipe or a processing substance introduction portion, or a combination of these with a heat exchanger and / or another heating device for heating a processing substance. Can be mentioned.

The apparatus for treating an organic chlorine compound according to the present invention may include a treated material discharging means for discharging the treated material from the treated material discharging portion to the outside. The discharge of the processed material from the processed material discharge unit includes, for example, discharge by extrusion with a fluid (a processing object, a processed material, a processing substance, or the like), discharge by suction using a suction device, discharge by gravity, various feeders. Discharge by a mechanical discharge device such as
Alternatively, it can be performed by a combination of two or more of these.

Further, the apparatus for treating an organic chlorine compound of the present invention comprises:
At least a product discharging means for discharging a product generated by subjecting at least the target organic chlorine compound to dechlorination and detoxification treatment by the processing gas from the product discharging section may be provided. The discharge from the product discharge section, such as products generated by subjecting the target organic chlorine compound to dechlorination treatment by the processing gas, is, for example, discharge by extrusion with the processing gas and / or suction by a suction device or the like. Can be carried out by discharging the wastewater.

The adsorption and detoxification treatment can be performed, for example, regardless of whether the object to be treated reaching the adsorbent is substantially gas or substantially solid. Can be mixed. It may contain ultrafine powder or the like.

The adsorption of the target organochlorine compound by the adsorbent may be a substance which is substantially liquid or contains a liquid when the treatment target reaches the adsorbent.

In particular, when the object to be treated can contain a liquid, it has a dry state detecting means for detecting the dry state of the adsorbent, and at least that the adsorbent is dried to a predetermined state or more. After the detection by the dry state detection means, it is desirable that the processing substance be supplied to the adsorbent. In this case and in other cases, a drying means for drying the adsorbent may be provided.

The dry state detecting means for detecting the dry state of the adsorbent includes, for example, a temperature sensor and / or 1 or 2 inside the processing unit or downstream of the processed material discharge section.
One or more sensors for detecting the above predetermined components are provided, and a computer or the like is used according to a change in temperature (for example, a sharp rise) detected by the temperature sensor and / or an amount or a ratio of the detected components. The determination can be made as an example.

The supply of the processing substance to the adsorbent is started after the dry state detecting means detects that the adsorbent has dried to a predetermined state or more (for example, the predetermined state or more is detected by the dry state detecting means). The supply of the processing substance to the adsorbent is started after the dry state is detected, for example, by opening an on-off valve.) Alternatively, for example, the supply may be performed before that.

Examples of the drying means include one or more of an electric heater using a heating wire, microwave irradiation, a decompression device, and the like.

The efficiency of adsorption of the target organic chlorine compound and detoxification of the adsorbed target organic chlorine compound by the hot gas for treatment is almost unchanged within the range of 150 to 600 ° C. Since the adsorbent is made of zeolite, the object to be treated has a high temperature (for example, 300 to 600).
° C), there is no danger of ignition or explosion as in the case of using activated carbon. Since the object to be treated can be treated at a high temperature of up to about 600 ° C., even when the object to be treated needs to be cooled before the adsorption treatment by the adsorbent, the required degree of cooling is lower than when using activated carbon. can do.

The target organic chlorine compounds include dioxins,
Dioxin precursors (eg, aromatic chlorine compounds such as benzene chloride, phenol chloride, naphthalene chloride, naphthol chloride, and diphenyl ether chloride, heat and / or
Or one or more selected from the group consisting of PCBs, and an organic chlorine compound capable of generating an aromatic chlorine compound by a catalytic reaction.
Other organochlorine compounds may be of interest.

Dioxins are defined as 2,3,7,8-tetrachlorodibenzo-para-dioxin (2,3,7,8-TCD
D), such as dibenzo-para-dioxins (Polychl
orinated dibenzo-p-dioxins), polychlorinated dibenzofurans, and coplanar PCBs (Coplanar polychlorinated biphenyls).

Other examples of dibenzo-para-dioxins include 1,2,3,7,8-PeCDD; 1,2,3,4,7,8-HxCDD;
3,6,7,8-HxCDD; 1,2,3,7,8,9-HxCDD; 1,2,3,4,6,7,8-Hp
CDD; 1,2,3,4,6,7,8,9-OCDD and the like can be exemplified.

As the dibenzofurans, 2,3,7,8-
TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,7,
8-HxCDF; 1,2,3,6,7,8-HxCDF; 1,2,3,7,8,9-HxCDF; 2,
3,4,6,7,8-HxCDF; 1,2,3,4,7,8,9-HpCDF; 1,2,3,4,6,7,
8-HpCDF; 1,2,3,4,6,7,8,9-OCDF and the like can be exemplified.

The coplanar PCBs are a group of PCBs (Polychlorinated biphenyls) having a flat structure.

As coplanar PCBs, 3,3 ', 4,4'-
TCB; 3,3 ', 4,4', 5-PeCB; 3,3 ', 4,4', 5,5'-HxCB; 2,3,
3 ', 4,4'-PeCB;2,3', 4,4 ', 5-PeCB; 2', 3,4,4 ', 5-PeCB;
2,3,4,4 ', 5-PeCB; 2,3,3', 4,4 ', 5-HxCB; 2,3,3', 4,4'5 '
-HxCB; 2,3,4,4 ', 5,5'-HxCB;2,3,3', 4,4 ', 5,5'-HpCB;
2,2 ', 3,3', 4,4 ', 5-HpCB; 2,2', 3,4,4 ', 5,5'-HpCB and the like can be exemplified.

PCBs are harmful substances designated as "first-class specific chemical substances" in the "Law Concerning Regulations on the Examination and Production of Chemical Substances (Chemical Substances Control Law)".
It is a generic term for a series of nine compound groups.

Under certain conditions (for example, a certain temperature range, specifically, 150 to 600 ° C.), decomposition or partial elimination of the target organic chlorine compound and an inert and / or reducing gas can occur. In the case of a substance which is easily formed, the target organochlorine compound thus formed is adsorbed on an adsorbent, and the target organochlorine compound is converted by the generated inert and / or reducing hot gas or by the generated hot gas. It is also possible to detoxify and detoxify by using another processing hot gas.

Examples of the object to be treated after reaching the adsorbent include those that are substantially gas, those that are substantially solid, and those that substantially consist of gas and solid.

Even if the liquid is introduced into the processing unit, it can be converted into a gas by vaporization or thermal decomposition before reaching the adsorbent. In this case, as a heating means for vaporization, thermal decomposition, or the like, a known heating means such as an electric heater using a heating wire or microwave irradiation can be appropriately used.

The object to be gas-treated includes a target organic chlorine compound as a gas and another gas (generally, for example, carbon dioxide or nitrogen).

The object to be solid-processed is a solid to which the target organic chlorine compound is adhered and / or contains the target organic chlorine compound (for example, metal fine particles, metal oxide fine particles, unburned carbon fine particles, powdery / granular particles). Or flaky metal or other inorganic or organic substances) and other solid substances.

The term "substantially gaseous" means not only the above-mentioned gas alone but also the above-mentioned solid particles (particularly fine solid particles) or droplets (particularly fine particles) in the above-mentioned gas. Droplets) and the like in a dispersed state or the like, but preferably do not contain solid particles or droplets (particularly, droplets).

The term "substantially solid" refers to a substance containing a small amount of a gaseous object or a liquid, but preferably does not contain these.

When the apparatus and method of the present invention are used, the object to be treated that has reached the adsorbent is 200 to 480.
C. is desirable. If necessary to achieve such a temperature, heating can be performed using an appropriate heating means.

The zeolite (Zeolite) may be a synthetic zeolite or a natural zeolite. The zeolite used as the adsorbent in the present invention has a fine pore of 6 to 1
It is desirable that the proportion of micropores having a pore size of 3 Å is as large as possible. Such zeolites can be used as target organochlorine compounds, especially dioxins and PC.
B can be adsorbed efficiently.

The zeolite used as the adsorbent is preferably, for example, a zeolite in which the pore size of 50% or more of the fine pores is 6 to 13 Å.

More preferably, the zeolite used as the adsorbent has a pore size of 80% or more of the micropores in the zeolite being 6 to 13 Å.
In this case, the zeolite can adsorb the target organic chlorine compound, particularly dioxins and PCBs, very efficiently. Examples of such synthetic zeolites include Z
SM-5 (pore size: about 7 angstroms) and FAUj
asite (pore diameter: about 7 angstroms). However, the proportion of micropores having a pore size of 6 to 13 angstroms in zeolite is 50%.
Even if it is less than (for example, about 10 to 30%), it can be used.

The zeolite has a Si /
It is desirable that Al has a hydrophobicity with an atomic ratio of 3 or more.

When the object to be treated can contain water in the form of droplets, it is possible to prevent the zeolite from adsorbing moisture earlier than the target organic chlorine compound, thereby preventing the adsorption ability of the target organic chlorine compound from being reduced. . In addition, since solid objects to be treated such as powders are often hydrophobic themselves,
Adsorption is easier when the adsorbent is hydrophobic.

The adsorbent inside the processing unit is, for example,
Zeolite formed in a multitubular aggregated structure, zeolite supported on the surface of a carrier with a multitubular aggregated structure, zeolite in a spongy porous structure, zeolite in a fibrous form, zeolite in a regular or irregular-shaped granular form, zeolite in a powder form, It may be one or two or more selected from the group consisting of zeolite in the form of a regular or irregular rod and zeolite in the form of a regular or irregular plate.

The multi-tube assembly structure is a structure in which a large number of tubes are assembled (for example, a structure in which the tubes are substantially parallel, that is, a parallel multi-tube assembly structure). Structure or corrugated cardboard structure of one or more steps (one or two or more flat plates and one or two or more corrugated plates are alternately laminated, and one Structure in which a large number of tubular portions are formed for each wavelength).

In particular, the adsorbent is a zeolite formed in a multitubular aggregated structure (for example, parallel multitubular aggregated structure) or a zeolite supported on the surface of a multitubular aggregated structure (for example, parallel multitubular aggregated structure). Some are preferred when the object to be treated is substantially a gas.

In the case where the object to be treated flows from the object introduction part to the treated matter discharge part in the treatment device, the zeolite or the carrier having the multi-tube assembly structure formed in the multi-tube assembly structure is substantially treated. It is rotatably supported and rotatably driven by a rotation drive mechanism so as to be rotatable around a rotation axis in the flow direction of the object, and has a large number of through holes through which the object to be processed can pass in the direction of the rotation axis. It is preferable that it is comprised by these. As a specific example,
A variety of honeycomb rotors in which zeolite is supported on the surface of a honeycomb structure can be given.

It is preferable that the adsorbent is provided in a plurality of places on the flow path of the processing object and the processing hot gas in the processing apparatus in different modes. For example, in the case of using a plurality of tubes each having a zeolite supported as an adsorbent on the surface of a carrier having a multitubular aggregate structure (parallel multitubular aggregate structure or the like), a zeolite having a different structure from the multitubular aggregate structure may be used. The distribution of the diameter of the micropores and the degree of hydrophobicity or hydrophilicity can be different. In addition, one multi-tube assembly structure (for example, a parallel multi-tube assembly structure)
The zeolite supported on the carrier may be varied as described above depending on the position of the multi-tube assembly structure (for example, the position in the direction in which the processing object and the processing hot gas flow).

When using the apparatus and method of the present invention, the adsorbent for the target organochlorine compound consisting of zeolite is 2
Within a predetermined temperature range of, for example, ± 20 ° C. in the range of 00 to 480 ° C. (for example, by the heat of an object to be treated or a substance to be treated introduced into the processor, or by an electric heater using heating wire, microwave irradiation, etc. (By other known means). When the object to be treated is substantially solid, it is desirable to maintain the temperature at 250 to 480 ° C. Maintaining the temperature can be performed while detecting the temperature using a temperature sensor as needed.

The processing substances can be inert gases and / or reducing gases. Of course, a substance which generates an inert gas and / or a reducing gas by thermal decomposition and / or catalytic decomposition before being supplied to the processor may be used.

Further, the processing substance supplied to the adsorbent in the processing unit by the processing substance supply means (or introduced into the processing unit from the processing substance source through the processing substance introduction unit) is thermally decomposed. A substance that generates reducing gases, or a substance that generates reducing gases by thermal decomposition, and an inert gas and / or a reducing gas as a processing gas. Before the substance reaches the adsorbent, a heating means for thermally decomposing the substance in the processor to generate reducing gases as a processing gas may be provided. As a heating means in that case, a known heating means such as an electric heater using a heating wire or microwave irradiation can be appropriately used.

The inert gases include, for example, nitrogen gas,
1 or 2 selected from the group consisting of helium gas, neon gas, argon gas, krypton gas and xenon gas
The above can be considered.

Examples of the reducing gas include a hydrogen gas and / or a carbon monoxide gas, and a temperature range (for example, 150 to 60) that can be used as a processing gas in the present invention.
0 ° C.) and those which are gases under pressure, such as various alcohols (eg, methanol, ethanol, propanol, butanol, etc.), organic acids (eg, formic acid, acetic acid, propionic acid, oxalic acid, etc.). . In addition, a compound containing carbon and hydrogen, which is a gas in a temperature range and a pressure that can be used as a processing gas in the present invention, may also be used.

Examples of the substance that generates reducing gases by the thermal decomposition include ammonia, amines, substances that generate ammonia and amines under use conditions, and hydrocarbons (eg, methane, ethane, propane, butane). Such as aliphatic hydrocarbons), organic acids (eg, formic acid, acetic acid, propionic acid, oxalic acid, etc.), alcohols (eg, methanol,
One or more selected from the group consisting of ethanol, propanol, butanol, etc., ketones (eg, acetone, ethyl methyl ketone), saccharides, and surfactants (anionic, cationic, or nonionic) Can be. Other compounds containing carbon and hydrogen may also be used.

The temperature of the processing hot gas that has reached the adsorbent can be, for example, 150 to 600 ° C.

The temperature of the processing hot gas is 150 ° C.
It is almost the lower limit temperature of the reaction for detoxifying the target organic chlorine compound, and 600 ° C. is almost the heat resistant temperature of zeolite as an adsorbent. More preferably, the temperature of the processing hot gas reaching the adsorbent is 250
To 500 ° C.

Further, the temperature of the processing gas as the processing substance that has reached the adsorbent is set to a temperature required for dechlorinating the target organic chlorine compound adsorbed by the adsorbent. And a heating means for heating the processing substance.

Such a heating means can be provided on the upstream side of the processing unit (processing substance introduction part) and / or in the processing unit, and a known heating unit can be appropriately used. Examples thereof include an electric heater using a heating wire and microwave irradiation. Further, a temperature sensor may be provided upstream of the processing unit (processing substance introduction unit) and / or at an appropriate position in the processing unit or the like, and heating may be performed by a heating unit according to the temperature detected by the temperature sensor.

(2) In the above apparatus for treating an organic chlorine compound, the supply of the processing gas to the adsorbent in the processing unit is performed after the supply of the processing object to the adsorbent in the processing unit is stopped. It can be.

After the supply of the processing object to the adsorbent in the processing unit is stopped after the supply of the processing object to the adsorbent in the processing unit is stopped, the target organic chlorine compound adsorbed by the adsorbent is supplied. Is efficiently dechlorinated and detoxified by the processing gas (processing hot gas at a required temperature). As mentioned above,
Part of the target organic chlorine compound adsorbed on the adsorbent may be decomposed depending on various conditions without using the processing hot gas.

Further, the supply of the processing gas to the adsorbent in the processing unit may be performed in whole or in part with the supply of the processing object to the adsorbent in the processing unit.

(3-1) In the apparatus for treating an organic chlorine compound, the treating device can accommodate the adsorbent therein in a movable state, and the treatment object which can contain the target organic chlorine compound is introduced into the object introduction section. From the adsorption treatment section introduced into the inside, and the dechlorination treatment section in which the treatment substance is introduced from the treatment substance introduction section, and at least the adsorbent, for transferring the adsorbent from the adsorption treatment section to the dechlorination treatment section A transport mechanism may be provided.

In this case, the target organochlorine compound which can be contained in the object to be treated is adsorbed by the adsorbent in the adsorption treatment section, and the adsorbent is transferred to the dechlorination treatment section by the transfer mechanism. The target organochlorine compound adsorbed by the adsorbent is dechlorinated and detoxified with high efficiency by the processing hot gas.

(3-2) As an example of the apparatus for treating an organic chlorine compound, the apparatus is provided with a transfer mechanism for transferring the dechlorinated adsorbent from the dechlorination section to the adsorption section. Can be.

In this case, it is possible to continuously perform the adsorption of the target organic chlorine compound on the object to be treated and the dechlorination harmless treatment while repeatedly using the adsorbent regenerated by the dechlorination treatment.

(3-3) As an example of the apparatus for treating an organic chlorine compound according to (3-1) or (3-2), the adsorbent may be a fibrous zeolite, a fixed or irregular shaped zeolite, or a powdery zeolite. One or more selected from the group consisting of zeolite, zeolite in the form of a fixed or irregular shaped rod, and zeolite in the form of a fixed or irregular shaped plate, and the object to be treated is substantially solid; A mixing device that mixes the zeolite with the object to be treated in the adsorption treatment part to adsorb the target organochlorine compound that can be contained in the object to be treated supplied into the adsorption treatment part by the part into the zeolite, and a zeolite; An example of the apparatus includes a separation device for separating the processed material.

In this case, a rotary kiln type can be used as the adsorption section provided with the mixing device, and the same can be used as the dechlorination section.

Further, it is possible to have a separation device for separating the treated object obtained by mixing the object to be treated with zeolite and carrying out the adsorption treatment and the zeolite. If necessary, the separated zeolite can be treated. The apparatus may have a feeding device for feeding a required portion such as a dechlorination section in the vessel.

(4) The above-mentioned organochlorine compound processing apparatus is an incinerator as a source of an object to be treated, and an apparatus for heating a substance to be treated to be a hot gas for processing. It may have a heat exchanger for heating the substance and / or another heating device, and the exhaust gas may be introduced into the processing unit through the object introduction part.

In this apparatus, the exhaust gas generated in the incinerator becomes an object to be treated (a solid object to be treated is dispersed in a gas object) and is introduced into the processing unit through the object introduction section. Solid waste generated in the incinerator (solid waste is so-called main ash, which is not ash that is scattered in the exhaust gas and discharged from the incinerator together with the exhaust gas, that is, fly ash) is regarded as the object to be treated. You can also.
A processing substance supplied from a processing substance source (a source of an inert gas, a reducing gas, or a substance that generates a reducing gas by thermal decomposition) is supplied to a heat exchanger and / or another heating device. And becomes a hot gas for treatment, which is used for dechlorination and detoxification of the target organic chlorine compound adsorbed by the adsorbent.

In this case, the apparatus for heating the processing substance into the processing hot gas is a heat exchanger for heating the processing object by the exhaust gas from the incinerator, or the heat exchanger and another heating apparatus. The exhaust gas that has passed through the heat exchanger may be introduced into the processor through the object introduction unit. However, even without such a heat exchanger or another heating device, such a heat exchanger or another heating device may be used if the processing substance reaching the adsorbent has a required temperature range. It is not always necessary to provide.

(5-1) The apparatus for treating an organic chlorine compound is as follows:
A processing device for gas, a processing device for solid, and a separation device for separating gas and solid in a processing target including gas and solid, and a substance obtained by separation by the separation device are provided. An object to be processed, which is a gas, is introduced into the gas processing unit through the object introduction unit, and the substantially solid object to be processed obtained by separation by the separation device is an object introduction unit. Through the solids treatment device.

In this case, before the object to be treated is introduced into the processor, the object to be treated is separated into a substantially gaseous object to be treated and a substantially solid object to be treated by a separation device. It is introduced to the processor and the processor for solids. Therefore, the target organochlorine compound which can be contained in the substantially gaseous treatment target and the target organochlorine compound which can be contained in the substantially solid treatment target are respectively adsorbed to the adsorbent in separate treatment units. Then, dechlorination treatment is performed by a processing hot gas.

When the separation treatment is performed as described above, metals such as Fe, Co, and Cu, which can be contained as solids in the object to be treated, are prevented from acting as a dioxin generation catalyst in a gas treatment device. In addition, regeneration of dioxins is effectively prevented.

For the separation device, for example, a bag filter, an electric dust collector or the like can be used. In that case, in order to increase the efficiency of the separation, it is desirable to cool the object to be treated before the separation and lower the temperature as necessary.

The object to be treated containing a gas and a solid may contain, for example, ultrafine powder. In this case, the ultrafine powder is separated by a separation device so that the ultrafine powder is separated from the gas side and the solid side. Any of them may be separated.

(5-2) The organochlorine compound treatment apparatus of (5-1) includes an incinerator as a source of an object to be treated and an incinerator as an apparatus for heating a substance to be treated into a hot gas for treatment. A heat exchanger for heating the processing substance with the exhaust gas from the furnace and / or
Or it may have another heating device, and the exhaust gas may be introduced into the separation device.

In this case, the exhaust gas generated in the incinerator becomes an object to be treated (a solid object to be treated such as solid particles dispersed in a gas object), and is introduced into the separation device and is subjected to the process of (5-1). The treatment can be performed in the same manner as in the organochlorine compound treatment apparatus.

The source of the substance for treatment and the substance for treatment are the same as those in the apparatus for treating an organic chlorine compound in the above (4).

Even without such a heat exchanger or another heating device, if the processing substance reaching the adsorbent is in a required temperature range, such a heat exchanger or another heating device may be used. Is not necessarily required.

(5-3) In the organochlorine compound treatment apparatus of (5-2), the apparatus for heating the treatment substance to produce a treatment hot gas heats the treatment substance by exhaust gas from an incinerator. Heat exchanger, or the heat exchanger and another heating device,
The exhaust gas cooled through the heat exchanger may be introduced into the separation device.

In this case, the exhaust gas of the incinerator is used for heating the processing substance, and at the same time, the exhaust gas is cooled. For this reason, it is effective to use a device having a relatively low temperature, such as a bag filter, having a high separation efficiency as a separation device. The exhaust gas may be further cooled if necessary and then introduced into a separation device such as a bag filter.

(5-4) In the apparatus for treating an organic chlorine compound according to (5-1) or (5-2), the solid discharged in the incinerator together with the solid separated by the separation device is supplied to the object introduction section. Through the solids treatment device.

In this case, the solid waste generated in the incinerator and the solid object to be treated such as solid particles that may be contained in the exhaust gas from the incinerator are both processed by the solid processing device, and the gas constituting the exhaust gas is a gas. It is processed by a processor.

(6-1) The apparatus for treating an organic chlorine compound is as follows:
A plurality of processing units, a processing unit into which a processing object is introduced through an object introduction unit, and a processing unit into which a processing substance is introduced through a processing substance introduction unit are configured so that both processing units are separate. In some processing units, a target organic chlorine compound that can be contained in the processing target introduced through the target introduction part is adsorbed by the adsorbent, and all other processing is performed. In the vessel or some other processing apparatus, the target organic chlorine compound adsorbed by the adsorbent is dechlorinated and detoxified by the processing hot gas as the processing substance introduced through the processing substance introduction section. Things.

The switching device includes a treatment device for introducing a treatment object through the treatment object introduction portion and adsorbing the target organic chlorine compound on the adsorbent therein, and a treatment substance introduction and adsorption through the treatment substance introduction portion. The treatment device for dechlorinating and detoxifying the target organic chlorine compound adsorbed on the agent can be sequentially switched so that both treatment devices (one or both may be plural) are separate. However, for example,
Instead of immediately introducing the processing substance into the processing unit into which the processing target has been introduced through the target introduction unit, after the required time for allowing the target organic chlorine compound to sufficiently adsorb to the adsorbent inside the processing unit, It can also be done.

Therefore, the adsorption of the target organic chlorine compound by the adsorbent in some of the processing units (one or two or more processing units) (or the supply of the processing target object to the adsorbent and the adsorption of the target organic chlorine compound by the adsorbent) And regeneration of the adsorption capacity of the target organic chlorine compound of the adsorbent by dechlorination and detoxification of the adsorbed target organic chlorine compound in all other processing units or some other processing units (one or more processing units). At the same time, the switching can also be performed sequentially. The earlier the timing of this switching, the higher the efficiency of adsorption of the target organic chlorine compound by the adsorbent. The time up to the switching depends on the specific device configuration, but can be, for example, 5 minutes to 24 hours. The switching timing is, for example, the adsorption state of the target organic chlorine compound by the adsorbent and / or the adsorption by the adsorbent. The dechlorination status of the target organic chlorine compound is made variable according to the result while monitoring components such as a treated product subjected to the adsorption treatment and / or a product of the dechlorination detoxification reaction by a sensor or the like. It is desirable.

Accordingly, a treatment device for adsorbing the target organic chlorine compound by the adsorbent (further, a treatment device for supplying the treatment object to the adsorbent and adsorbing the target organic chlorine compound by the adsorbent, It can be divided into a treatment device that performs only adsorption) and a treatment device that detoxifies and detoxifies the adsorbed target organic chlorine compound (for example, one of the two treatment devices is switched over for a certain period of time to the target organic chlorine compound). The other is used for the regeneration of the adsorption capacity of the target organic chlorine compound for adsorption, and the two processing units are switched over and used repeatedly for the next fixed time), and the adsorption processing and the dechlorination detoxification processing of the target organic chlorine compound generated are performed. , Respectively.

The switching device for switching between the processing device for introducing the processing object through the object introduction portion and the processing device for introducing the processing substance through the processing substance introduction portion includes:
For example, an on-off valve is provided in each of the object introduction section and the processed material discharge section and the processing substance introduction section and the product discharge section in each processor, and the on-off control of these on-off valves (for example, the introduction of the processing object is performed). Regarding the processor that opens the on-off valve of the object introduction section and the processed material discharge section, closes the on-off valve of the processing substance introduction section and the product discharge section, and introduces the processing substance, Close the on-off valves of the object introduction section and the processed material discharge section, and open the on-off valves of the processing substance introduction section and the product discharge section, or introduce the object in the case of the processing device that introduces the processing object. Open the on-off valve of the section, close each on-off valve of the processing substance introduction section, product discharge section, and processed substance discharge section, and for the processing unit that introduces the processing substance, the object introduction section and processed substance discharge. Close each on-off valve Both Open the valves of the processing material introduction portion and products such discharge unit opens the closing valve of the processed material discharging section after dechlorination detoxification.) Makes it possible to include those to perform the switching.

(6-2) The apparatus for treating an organochlorine compound of (6-1) is provided with a plurality of gas treatment units and solid treatment units, or a gas treatment unit or a solid treatment unit. The apparatus is a plurality, for a plurality of gas or solid processing devices, a processing device that introduces a processing object through the object introduction unit, a processing device that introduces a processing substance through the processing substance introduction unit, It is equipped with a switching device that can be sequentially switched so that both processing units are separate, in some of the plurality of existing gas or solid processing units, through the target introduction unit The target organochlorine compound that may be contained in the introduced treatment target is adsorbed by the adsorbent, and in all or some other treatment units among the plurality of gas or solid treatment units. Is the pair adsorbed on the adsorbent Organochlorine compounds, can be assumed to be processed dechlorinated harmless by treatment for hot gas as a process for material introduced through the processing material introduction portion.

In this case, similarly to the organochlorine compound treating apparatus of (5-1), the gaseous organochlorine compound which can be contained in the substantially gaseous treatment object and the substantially solid treatment object are included. The solid target organochlorine compounds that can be included are respectively adsorbed to the adsorbent in separate processing units, and further subjected to dechlorination detoxification processing by the processing hot gas, so that Fe, Co that can be included as solids in the processing target object , A metal such as Cu,
It does not act as a catalyst for forming dioxins in the gas treatment unit, and regeneration of dioxins is effectively prevented. Similarly, as in the organic chlorine compound treatment apparatus (6-1), a processor for adsorbing the target organic chlorine compound by the adsorbent and a processor for dechlorinating the adsorbed target organic chlorine compound are sequentially arranged. By switching, the adsorption treatment and the dechlorination detoxification treatment of the generated target organic chlorine compound can be performed, for example, continuously, respectively.

The timing of switching by the switching device can be the same or independent for the gas processing unit and the solid processing unit.

(7) The apparatus for treating an organic chlorine compound introduces the discharge discharged from the product discharge section of the processor,
By dispersing a solvent (eg, water, alcohol, petroleum solvent, etc.) or a solvent mixture obtained by mixing [acid or alkali] and / or [oxidizing or reducing agent] in the solvent, It may have a harmful gas removing section for removing harmful gases that may be present in the effluent by the solvent or the solvent mixture.

The harmful gas (chlorine gas, phosphorus compound gas, etc.) that may be present in the effluent discharged from the product discharge section of the processor is removed in the harmful gas removal section. Specifically, a scrubber can be used as such a harmful gas removing unit.

[0102]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic diagram of a dioxin and its precursor processing apparatus as an example of an embodiment of the present invention. Note that the processing device described below is a PC
It can also be used for the treatment of Class B and other organochlorine compounds.

This processing apparatus includes an incinerator 10 (source of processing target) equipped with a burner 10a to which fuel and combustion air are supplied, a nitrogen gas supply device 12 (processing substance source), and a heat source for heating nitrogen gas. Exchanger 14, exhaust gas cooling device 16, bag filter 18 (separation device), lime supply unit for supplying lime to bag filter 18, high pressure air supply unit for back washing of bag filter 18, three gas treatment units 20 A gas processing device 22 comprising a gas processing device switching device (not shown), a solid processing device 26 comprising two solid processing devices 24 and a solid processing device switching device (not shown), a treated ash filter 28, mercury removal and cooling device 30, detoxified ash bucket 32, treated ash filter 28, high-pressure air supply unit for backwashing, scrubber 34 for dechlorination gas supplied with water for scrubber, water neutralization device 3 , Exhaust fan 38, and the chimney 4
It has zero.

The gas treatment unit 20 is composed of two adsorbing layers in which zeolite is carried as an adsorbent on the surfaces of two carriers having different honeycomb structures in a cylindrical body 20a having both ends reduced in diameter. 20b and 20c are provided at different positions in the axial direction. Each adsorption layer 20b
The zeolites in 20c may be the same or different. The three gas processors 20 have the same configuration. Such a gas processor 20 may be a horizontal type as shown in FIG. 2 or a vertical type as shown in FIG. In the case of the vertical type, each adsorption layer 2
Ob and 20c may be supported on a net-like support shelf 20d, for example. In this case, the flow direction of the processing target gas and the hot nitrogen gas (processing hot gas) may be upward or downward. The number of the adsorbing layers 20b and 20c is 2
However, the number is not limited to 1, and may be 3 or more. Further, a part or all of the adsorption layers 20b and 20c may be formed as a honeycomb rotor in which zeolite is supported on the surface of a honeycomb structure.

Each gas processor 20 is branched at its front into a target gas introduction section 20e (target substance introduction section) and a hot nitrogen gas introduction section 20f (processing substance introduction section). And an on-off valve 42 for hot nitrogen gas introduction. In addition, each gas processing unit 20
Is divided into a processed material discharge section 20g and a product discharge section 20h at the rear thereof, and a processed material discharge opening / closing valve 46 and a product discharge section open / close valve 48 are provided respectively.

The switching device for the gas processor includes an on-off valve 42 for the target gas introduction unit, an on-off valve 44 for the hot nitrogen gas introduction unit, and an on-off valve 4 for the processed material discharge unit for each of the gas treatment units 20.
6 and a control device for controlling the opening / closing of a product discharge opening / closing valve 48. For any one of the gas processors 20, the hot nitrogen gas introduction opening / closing valve 44 and the product discharge section The on / off valve 48 for the target gas introduction unit and the on / off valve 46 for the processed material discharge unit are closed, and the on / off valve 42 for the target gas introduction unit and the processing for the other two gas processing units 20 are closed. The open / close valve 46 for the waste product discharge section is opened, and the open / close valve 44 for the hot nitrogen gas introduction section and the open / close valve 48 for the product discharge section are closed. The gas processor 20 that opens the on-off valve 44 for the hot nitrogen gas introduction section and the on-off valve 48 for the product discharge section
Are sequentially switched at predetermined time intervals.

The solid processing unit 24 is a fluidized bed processing unit that forms a fluidized bed with zeolite particles on an airflow deck in a container. The solid processing unit 24 has a target ash introduction unit 24a (target object) having a target ash introduction unit on-off valve 50. Introduction section), a hot nitrogen gas introduction section 24b (a processing substance introduction section) having a hot nitrogen gas introduction section opening / closing valve 52, and a processed product and products discharge section 24c (a processed product discharge section and a product). Class discharge unit).

The switching device for the solid processing device has a control device for controlling the on-off valve 50 for the target ash introduction unit and the on-off valve 52 for the hot nitrogen gas introduction unit for each solid processing unit 24. The open / close valve 52 for the hot nitrogen gas introduction section of the processing unit 24 is opened, and the open / close valve 50 for the target ash introduction section is opened.
Is closed, and the on-off valve 50 for the target ash introduction unit is opened for the other solid processing unit 24, and the on-off valve 52 for the hot nitrogen gas introduction unit is closed. The solid processing unit 24 that opens the hot nitrogen gas introduction unit on-off valve 52 is sequentially switched at predetermined intervals.

Exhaust gas (including solids to be treated such as solid particles) generated by incineration of the incinerator in the incinerator 10 is passed through a heat exchanger 14 for heating nitrogen gas and an exhaust gas cooling device 16 to be discharged to the incinerator 10. After cooling to ± 20 ° C
The gas is introduced into the bag filter 18 and separated into a gas to be processed and a solid processing object (fly ash).

The gas to be treated is supplied to the two gas treatment units 2 in which the target gas introduction part opening / closing valve 42 and the processed material discharge part opening / closing valve 46 are opened by the gas treatment unit switching device.
0, through the target gas introduction unit 20e,
0b and 20c. Dioxins and their precursors in the gas to be treated are adsorbed on zeolite in each of the adsorption layers 20b and 20c. The treated gas subjected to the adsorption treatment is discharged from the treated material discharge section 20g, is sucked by the exhaust fan 38 via the dechlorination gas scrubber 34, and is exhausted from the chimney 40.

The nitrogen gas supplied from the nitrogen gas supply device 12 is heated by the exhaust gas in the heat exchanger 14 for heating the nitrogen gas to become hot nitrogen gas of about 300 to 500 ° C. A portion of this hot nitrogen gas is transferred to one gas processor 20 in which the hot nitrogen gas inlet / outlet valve 44 and the product discharge port on / off valve 48 are opened by the gas processor switching device. The gas is introduced through the gas introduction part 20f and guided to the adsorption layers 20b and 20c. The adsorption layer 20b
If the dioxins or their precursors in the gas to be treated are previously adsorbed to c, the dioxins or their precursors are dechlorinated and detoxified by hot nitrogen gas,
Desorbs from zeolite. Products such as chlorine gas and nitrogen gas by this reaction are discharged from the product discharge section 20h. By thus detoxifying and desorbing the dioxins and their precursors, the adsorption capacity of zeolite as an adsorbent is regenerated and can be used repeatedly. In addition, since detoxification is performed by hot nitrogen gas, regeneration of dioxins can be prevented with high certainty.

After the chlorine gas and the like discharged from the product discharge section 20h and the nitrogen gas and the like are removed by the dechlorination gas scrubber 34, the exhaust fan 3
8 and is exhausted from the chimney 40. The water containing hydrochloric acid by removing the chlorine gas by using the dechlorination gas scrubber 34 is neutralized by alkali in the water neutralization device 36 and then discharged.

The object to be solid-processed (fly ash) is fed to the solid-state processing device 24 using a feeder such as a screw conveyor and the like, and the target-ash-introducing opening / closing valve 50 is opened by the solid-processing device switching device. Introduced through the target ash introduction part 24a,
It is led to a fluidized bed for adsorption by zeolite particles. The dioxins and their precursors that have adhered to and / or are contained in the solid processing target are adsorbed to the zeolite particles in the fluidized bed for adsorption. The treated ash that has been subjected to the adsorption treatment is discharged from the treated product and products discharge section 24c, the ash is separated in the treated ash filter 28, and is passed through the mercury removal and cooling device 30 to the harmless ash bucket 32. Is discharged. The gas separated in the treated ash filter 28 passes through a dechlorination gas scrubber 34 and exhaust gas 3
8 and is exhausted from the chimney 40.

A part of the hot nitrogen gas is transferred to the solid processing device 24 in which the hot nitrogen gas inlet opening / closing valve 52 is opened by the solid processing device switching device.
b and is led to a fluidized bed for adsorption by zeolite particles. If the dioxins or their precursors adhering to and / or incorporated into the solid processing target are previously adsorbed on the zeolite particles of the fluidized bed for adsorption, the dioxins or their precursors are desorbed by hot nitrogen gas. Detoxified by chlorine and desorbed from zeolite. Products such as chlorine gas and nitrogen gas by this reaction are discharged from the treated product and products discharge section 24c, and after the chlorine gas is removed by the scrubber 34 for dechlorination gas, it is sucked by the exhaust fan 38. Exhaust from the chimney 40.

In this way, the dioxins and their precursors which can be contained in the gas to be treated and the dioxins and their precursors which can be contained in the solid object to be treated are separated into zeolites, which are adsorbents, in separate processors. , And further subjected to dechlorination detoxification treatment with hot nitrogen gas, so that Fe, which can be contained as a solid in the solid processing object,
Metals such as Co and Cu are prevented from acting as dioxin generation catalysts in the gas treatment device, and regeneration of dioxins is effectively prevented. In addition, while continuously operating the incinerator, etc., which is the source of the object to be treated, a treatment device that adsorbs dioxins and their precursors with an adsorbent, and a dechlorinating detoxification of the adsorbed dioxins and their precursors. By sequentially switching the processing units to be performed, the adsorption treatment and the dechlorination detoxification treatment of the generated dioxins and their precursors can be continuously performed.

The solid processing device 26 can be replaced with a solid processing device 70 shown in FIG.

The object to be solid-treated (fly ash) is a fly ash hopper 6
After being stored in the ash hopper 60, the fly ash is supplied to the screw conveyor 62 via the quantitative supply device 60 a provided in the fly ash hopper 60. The object to be solid-processed sent by the screw conveyor 62 is supplied to one end of a rotary kiln 72 for adsorption processing with a heating device in the processing apparatus 70 for solid through a rotary valve 64. The zeolite grains inside the rotary kiln 72 for the adsorption treatment and the solid treatment target are:
The mixture is conveyed toward the other end of the rotary kiln 72 for adsorption while being mixed while being heated in the rotary kiln 72 for adsorption. As a result, the dioxins and their precursors attached to and / or incorporated in the solid processing target are adsorbed on the zeolite particles.

The zeolite particles discharged from the other end of the rotary kiln 72 for adsorption processing and the processed material subjected to the adsorption processing are sorted by a sorting device 76 (for example, by means of wind separation) through a rotary valve 74, and the processed products are treated. Things are
It is conveyed while being cooled by the cooling conveyor 78, and is discharged to the harmless ash bucket 32 through the mercury removing and cooling device 30.

On the other hand, the zeolite grains are sorted by the sorting device 76 and stored in the zeolite hopper 80, and then supplied to one end of a rotary kiln 82 for dechlorination with a heating device, and heated toward the other end while being heated inside. Transported. During this time, the dioxins and / or their precursors adsorbed on the zeolite particles are dechlorinated and detoxified by the hot nitrogen gas supplied from the other end of the dechlorination rotary kiln 82, and detoxified from the zeolite particles. Let go. Chlorine gas due to this reaction, products resulting from the desorption of chlorine gas, nitrogen gas, and the like are supplied from one end of the rotary kiln 82 for dechlorination to the treated ash filter 2.
It is discharged to 8.

The regenerated zeolite particles from which the dioxins and / or their precursors have been desorbed are discharged from the other end of the rotary kiln 82 for dechlorination, and the rotary valve 84 and the zeolite hopper 86
Is fed to one end of the rotary kiln 72 for adsorption treatment and reused. Therefore, it is possible to continuously perform the adsorption and dechlorination detoxification of the target organic chlorine compound on the object to be treated while repeatedly using the adsorbent regenerated by the dechlorination treatment.

It is also possible to introduce a solid discharge (main ash) generated in an incinerator together with the solid processing object (fly ash) into a solid processing device for processing.

The solid processing device 26 can be replaced with a solid processing device 90 shown in FIG.

The solid processing object (fly ash) accommodated in the fly ash hopper 60 is supplied to the screw conveyor 62 via the quantitative supply device 60a, and is passed through the rotary valve 64.
The processing device 1 is controlled by the distribution valve 92 in the solid processing device 90.
It is sequentially distributed to 00, 200, and 300.

The zeolite grains are stored on the airflow decks 101, 201, 301 in the respective processors 100, 200, 300.

Each of the processors 100 and 200 passes through the distribution valve 92.
The object introduction units 102, 202, and 302 for introducing the solid processing object into the upper part of the 300 are provided with on-off valves 104, 204, and 304 for the object introduction unit, respectively.

The chlorine gas desorbed from the zeolite particles, and the products generated by the desorption of the chlorine gas, and the nitrogen gas, etc., are discharged from the upper ends of the processors 100, 200, and 300 to the treated ash filter 28. Material discharge unit 106.2
06, 306 are provided, and the product discharge sections 106, 20 are provided.
The first on-off valve 10 is provided on each of the processing units 100, 200, and 300 and the processed ash filter 28 on the side of the processing ash 6 and 306.
8.208.308 and second on-off valve 110.210.3
10 are provided.

Further, each product discharge section 106, 206,
Each processing unit 10 is connected between the first on-off valve 108, 208, 308 and the second on-off valve 110, 210, 310 at 306.
0, 200, 300 (airflow deck 101, 20)
1) (circle below 1 ・ 301)
12, the third on-off valves 114, 214, 314, the blowers 116, 216, and the blowers 116, 216, and 316 in order from the product discharge units 106, 206, and 306 toward the lower ends of the processors 100, 200, and 300, respectively. 316 and the fourth on-off valve 118.2
18.318 are provided. Each circulation section 112 ・ 21
Third on-off valve 114, 214, 314 at 2.312
The hot nitrogen gas is supplied between the blowers 116, 216, and 316 via hot nitrogen gas introduction on-off valves 120, 220, and 320, respectively.

Further, the processed material discharge sections 122, 222, and 32 for discharging the processed material on which the solid processing object has been processed downward from the lower ends of the processing units 100, 200, and 300.
2, the on-off valves 124, 224, 324 for the treated material discharge section
Is provided.

The solid processing object is accommodated in the processing unit 100, and the dioxins and their precursors attached to and / or incorporated in the previously stored solid processing object in the processing unit 200 constitute a fluidized bed. When the dioxins and / or their precursors adsorbed on the zeolite particles are dechlorinated and detoxified in the treatment device 300 by adsorbing the zeolite particles, the treatment can be performed as follows. The switches are sequentially switched by a switching device (not shown) that controls the opening and closing of the distribution valve 92 and other on-off valves and the operation and stop of the blowers 116, 216, and 316. That is, the processor 100, the processor 200, and the processor 300 execute and in the next step, respectively, and are executed in the next step, and in the next step, and are executed again. You.

Open the on-off valve 104 for the object introduction part,
While closing the on-off valves 204 and 304 for the object introduction part,
The blower 116 is stopped, and the first on-off valve 108, the second on-off valve 110, the third on-off valve 114, the fourth on-off valve 118, the on-off valve 120 for introducing hot nitrogen gas, and the on-off valve 124 for the processed material discharge section are turned off. By closing, the object to be solid-processed is sent to the processor 100 by the distribution valve 92 and the airflow deck 101
Can be housed on top. In the meantime, at least a part of the dioxins and their precursors attached to and / or incorporated in the solid processing object are adsorbed on the zeolite particles constituting the fluidized bed.

First on-off valve 208, third on-off valve 214
And the fourth on-off valve 218 is opened, and the on-off valve 2 for the object introduction section is opened.
04, second on-off valve 210, on-off valve 22 for introducing hot nitrogen gas
0 and the on-off valve 224 for the treated material discharge section, and the blower 2
By operating 16, a fluidized bed of zeolite particles is formed above the airflow deck 201 while the atmosphere in the processing unit 200 is circulating, and the contained solid processing target and the zeolite particles are sufficiently mixed to form a solid. Dioxins and / or their precursors adhering to and / or contained in the object to be treated are adsorbed on the zeolite particles.

First on-off valve 308, second on-off valve 31
0, third on-off valve 314, on-off valve 32 for introducing hot nitrogen gas
0 and the fourth on-off valve 318 are opened, the on-off valve 304 for the object introduction section and the on-off valve 324 for the processed material discharge section are closed, and the blower 316 is operated. On / off valve 32 for hot nitrogen gas introduction
The hot nitrogen gas blown from below the airflow deck 301 in the processor 300 via the 0 and the fourth on-off valve 318 causes the zeolite particles adsorbing dioxins and their precursors to form a fluidized bed, and the hot nitrogen gas causes The dioxins and / or their precursors adsorbed on the zeolite particles are dechlorinated and made harmless, and desorbed from the zeolite particles. The chlorine gas due to this reaction, the product resulting from the desorption of chlorine gas, nitrogen gas and the like are supplied to the first on-off valve 30.
8 and the second on-off valve 310, the treated ash filter 28
Is discharged to

After the dechlorination and detoxification treatment of the dioxins and / or precursors thereof adsorbed on the zeolite granules is completed, the treated material is opened and closed to remove mercury and to remove mercury. It is discharged to the harmless ash bucket 32 through the cooling device 30.

[0134]

EXAMPLE According to the present invention, dibenzo-para-dioxins in fly ash (collected from ash contained in exhaust gas from an incinerator) are adsorbed on zeolite (ZSM-5) and then adsorbed on the zeolite. Was treated in a nitrogen gas atmosphere at 300 ° C. to dechlorinate and decompose dibenzo-para-dioxins. The dibenzo-para-dioxins were classified according to the number of chlorine atoms (Cl _x ) (where x is 4,
5, 6, 7, or 8), elapsed time (0 hour [non treated], 1 hour [1Hr], 2 hours [2Hrs],
The results of measuring the concentration (vertical axis: ng / g) every 4 hours [4Hrs]) are shown in the graph of FIG. In addition, <1 shows that it is less than 1.

As comparative examples, dibenzo-para-dioxins (PCDDs) in fly ash collected from the same ash (having a chlorine atom number of 8 [OCDD], 7 [H7CDD], 6 [H6CDD], 5 [P5CDD] ,
4 [T4CDD]) is adsorbed on zeolite (ZSM-5), and the zeolite is heated at 250 ° C., 300 ° C. and 350 ° C.
C. for 1 hour in each air atmosphere at
The results of measuring the concentration (ng / g) of para-dioxins for each dibenzo-para-dioxin chloride are shown in the table of FIG. The column of non treated is the concentration of untreated dibenzo-para-dioxins.

Note that T4CDD, P5CDD, H6CDD, H7C in FIG.
DD and OCDD correspond to Cl _x in FIG. 6 where x is 4, 5, 6, 7, and 8, respectively.

[0137]

According to the present invention, the target organochlorine compound which can be contained in the object to be treated is adsorbed by the adsorbent made of zeolite, and in such a state, the inert and / or reducing treatment is carried out. It is made harmless by dechlorination with hot gas and desorbed from the adsorbent. As a result, the ability of the adsorbent to adsorb the target organic chlorine compound is regenerated, and the adsorbent can be used repeatedly. Since dechlorination and detoxification are performed by the inert and / or reducing heat gas for treatment, regeneration of the target organic chlorine compound can be prevented with high reliability.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for treating dioxins and precursors thereof.

FIG. 2 is an explanatory view of a horizontal gas processing device.

FIG. 3 is an explanatory view of a vertical gas processor.

FIG. 4 is a diagram illustrating an example of a solid processing apparatus.

FIG. 5 is an explanatory view of another example of the solid processing apparatus.

FIG. 6 is a graph showing the concentration of dioxins after decomposition in a nitrogen atmosphere.

FIG. 7 is a table showing the concentration of dioxins formed after the formation in an air atmosphere.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Incinerator 10a Burner 12 Nitrogen gas supply device 14 Heat exchanger 16 Exhaust gas cooling device 18 Bag filter 20 Gas processor 20a Cylindrical body 20b Adsorption layer 20c Adsorption layer 20d Support shelf 20e Target gas introduction part 20f Hot nitrogen gas introduction part 20g Treated matter discharge section 20h Product discharge section 22 Gas treatment device 24 Solid processing device 24a Target ash introduction section 24b Hot nitrogen gas introduction section 24c Treated product and product discharge section 26 Solid treatment device 28 Treated Ash filter 30 Cooling device 32 Detoxification ash bucket 34 Scrubber for dechlorination gas 36 Water neutralization device 38 Exhaust fan 40 Chimney 42 Open / close valve for target gas introduction unit 44 Open / close valve for hot nitrogen gas introduction unit 46 Treated product discharge unit On-off valve 48 On-off valve for product discharge section 50 On-off valve for target ash introduction section 52 Introducing hot nitrogen gas Part on-off valve 60 Fly ash hopper 60a Quantitative supply device 62 Screw conveyor 64 Rotary valve 70 Solid processing unit 72 Rotary kiln 74 for adsorption treatment 74 Rotary valve 76 Sorting device 78 Cooling conveyor 80 Zeolite hopper 82 Rotary kiln 84 for dechlorination treatment 84 Rotary valve 86 Zeolite hopper 90 Solid processing unit 92 Distributing valve 100 Processor 101 Airflow deck 102 Object introduction unit 104 Object introduction unit on-off valve 106 Product discharge unit 108 First on-off valve 110 Second on-off valve 112 Circulation unit 114 First 3 on-off valve 116 blower 118 4th on-off valve 120 on-off valve for introducing hot nitrogen gas 122 processed material discharge section 124 on-off valve for processed material discharge section 200 processor 201 airflow deck 202 object introduction section 204 for object introduction section On-off valve 206 Product discharge section 208 First open / close valve 210 Second open / close valve 212 Circulation section 214 Third open / close valve 216 Blower 218 Fourth open / close valve 220 Open / close valve for introducing hot nitrogen gas 222 Treated matter discharge section 224 Treated matter discharge Part on-off valve 300 Processor 301 Airflow deck 302 Object introduction part 304 Object introduction part on-off valve 306 Product discharge part 308 First on-off valve 310 Second on-off valve 312 Circulation part 314 Third on-off valve 316 Blower 318 Fourth on-off valve 320 On-off valve for introducing hot nitrogen gas 322 Treated material discharge part 324 On-off valve for treated material discharge part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 25/18 B01D 53/34 134E // C07D 319/24 B09B 5/00 ZABN (72) Inventor Hiroo Fukushima 9-3-21 Honcho, Toyonaka-shi, Osaka (72) Inventor Takashi Kawagishi 4- 1-9 Yamatohigashi, Kawanishi-shi, Hyogo F-term (reference) 4D002 AA21 AC04 BA02 BA04 BA12 BA14 CA07 CA09 CA13 DA01 DA45 EA01 EA04 EA05 EA08 GA01 GA02 GA03 GB03 GB08 GB11 GB12 GB20 HA08 4D004 AA37 AB03 AB06 AB07 CA12 CA22 CA42 CA47 CB05 CB31 CB42 CB43 CC04 DA01 DA02 DA03 DA06 DA20 4H006 AA02 AC13 AC26 AD17 BB61 BE20 BE40 DA10 DA25 DA46 EA13

Claims (45)

[Claims] 1. A processing device having therein an adsorbent for a target organic chlorine compound made of zeolite, and a processing object supply means for supplying a processing object that can contain the target organic chlorine compound to the adsorbent And a processing substance supply means for supplying an inert and / or reducing processing gas to the adsorbent as a processing substance for dechlorinating the target organic chlorine compound adsorbed on the adsorbent. An organic chlorine compound processing apparatus, wherein the processing gas having reached the adsorbent is a processing hot gas at a temperature at which the target organic chlorine compound adsorbed by the adsorbent can be dechlorinated. 2. A processing object source, which is a supply source of a processing object that may contain a target organochlorine compound, and a processing object supplied from the processing object source is introduced into the processing unit and An object introduction section for leading to the adsorbent, a treated substance discharge section for discharging a treated substance obtained by subjecting the treated object to the adsorption treatment of the target organochlorine compound from the treatment device, and an adsorbent. A treatment substance source, which is a supply source of the treatment substance for detoxifying and detoxifying the target organic chlorine compound adsorbed on the substrate, and a treatment substance supplied from the treatment substance source are introduced into the treatment unit. It has a treatment substance introduction section for leading to the adsorbent, and a product discharge section for discharging at least a product produced by dechlorination and detoxification of the target organic chlorine compound by the treatment substance from the treatment device. And the processing substance that has reached the adsorbent Organochlorine compound according to claim 1, wherein the inert and / or reducing treatment for hot gas having a temperature of target organic chlorine compounds adsorbed by the adsorbent may dechlorination treatment apparatus. 3. An object introduction part, a treatment substance introduction part, a treated material discharge part, and a product discharge part are respectively separate, or any two are common and the other two are separate. The apparatus for treating an organochlorine compound according to claim 2, wherein any two and the remaining two are common, any three are common, or all are common. 4. The target organic chlorine compound is a dioxin,
4. One, two or more selected from the group consisting of dioxin precursors and PCBs.
An apparatus for treating an organic chlorine compound as described in the above. 5. The apparatus for treating an organochlorine compound according to claim 1, wherein the treatment object having reached the adsorbent is substantially a gas. 6. The apparatus for treating an organochlorine compound according to claim 1, wherein the treatment object having reached the adsorbent is substantially solid. 7. The apparatus for treating an organic chlorine compound according to claim 1, wherein the object to be treated having reached the adsorbent is substantially composed of gas and solid. 8. A dry state detecting means for detecting a dry state of the adsorbent, wherein at least after the dry state detecting means detects that the adsorbent is dried to a predetermined state or more, the dry state is detected. The apparatus for treating an organochlorine compound according to claim 1, wherein the treatment substance is supplied. 9. The apparatus for treating an organic chlorine compound according to claim 1, further comprising a drying means for drying the adsorbent. 10. The apparatus for treating an organochlorine compound according to claim 1, wherein the pore diameter of 50% or more micropores in the zeolite is 6 to 13 Å. 11. The apparatus for treating an organochlorine compound according to claim 1, wherein the pore diameter of 80% or more of the micropores in the zeolite is 6 to 13 Å. 12. The method according to claim 1, wherein the zeolite has a Si content in its component.
The organic chlorine compound treating apparatus according to any one of claims 1 to 11, wherein the value of the atomic ratio of / Al is 3 or more. 13. A zeolite formed in a multitubular aggregated structure, a zeolite supported on a surface of a carrier having a multitubular aggregated structure, a zeolite having a spongy porous structure, and a fibrous zeolite. One or more selected from the group consisting of zeolite in the form of regular or irregular granules, zeolite in the form of powder, zeolite in the form of rods in the form of regular or irregular forms, and zeolite in the form of regular or irregular plates. 13. The apparatus for treating an organic chlorine compound according to any one of 1 to 12. 14. An apparatus for treating an organic chlorine compound according to claim 1, wherein the processing substance is an inert gas and / or a reducing gas. 15. The processing substance introduced into the processing unit from the processing substance source through the processing substance introduction part is a substance that generates reducing gases by thermal decomposition or a substance that generates reducing gases by thermal decomposition. And an inert gas and / or a reducing gas as a processing gas, wherein the substance which generates the reducing gas by the thermal decomposition is thermally decomposed in the processing device before reaching the adsorbent. The apparatus for treating an organic chlorine compound according to any one of claims 2 to 14, further comprising a heating means for generating reducing gases as a processing gas. 16. The organic chlorine compound according to claim 14, wherein the inert gas is at least one selected from the group consisting of nitrogen gas, helium gas, neon gas, argon gas, krypton gas, and xenon gas. Processing equipment. 17. The apparatus for treating an organic chlorine compound according to claim 14, wherein the reducing gas is a hydrogen gas and / or a carbon monoxide gas. 18. The method according to claim 1, wherein the substance that generates reducing gases upon thermal decomposition is one or more selected from the group consisting of ammonia, amines, hydrocarbons, organic acids, alcohols, ketones, sugars, and surfactants. The apparatus for treating an organic chlorine compound according to claim 15, wherein the number is two or more. 19. The temperature of a processing gas as a processing substance having reached the adsorbent is set to a temperature necessary for dechlorinating the target organic chlorine compound adsorbed by the adsorbent. 19. The apparatus for treating an organochlorine compound according to claim 1, further comprising heating means for heating the treatment substance. 20. The apparatus for treating an organic chlorine compound according to claim 1, wherein the temperature of the processing gas having reached the adsorbent is 150 to 600 ° C. 21. The method according to claim 1, wherein the supply of the processing gas to the adsorbent in the processing unit is performed after the supply of the processing target to the adsorbent in the processing unit is stopped. Organic chlorine compound processing equipment. 22. The method according to claim 1, wherein the supply of the processing gas to the adsorbent in the processing unit is performed entirely or partially in parallel with the supply of the processing target to the adsorbent in the processing unit. An apparatus for treating an organic chlorine compound according to any one of the above. 23. An adsorption treatment section, wherein the treatment device is capable of accommodating the adsorbent therein in a movable state, and a treatment object capable of containing the target organic chlorine compound is introduced from the object introduction portion into the inside, A dechlorination section in which the processing substance is introduced from the processing substance introduction section into the inside, and a transfer mechanism for transferring at least the adsorbent from the adsorption section to the dechlorination section. 23. The apparatus for treating an organic chlorine compound according to any one of 2 to 22. 24. An incinerator as a source of an object to be treated, and an apparatus for heating a substance to be treated into a hot gas for treatment,
24. The apparatus according to claim 2, further comprising a heat exchanger and / or another heating device for heating the processing substance with the exhaust gas from the incinerator, wherein the exhaust gas is introduced into the processor through the object introduction unit. An apparatus for treating an organic chlorine compound as described in the above. 25. An apparatus for heating a treatment substance into a treatment hot gas by using a heat exchanger for heating the treatment substance by exhaust gas from an incinerator, or a heat exchanger and another heating apparatus. 25. The apparatus for treating an organic chlorine compound according to claim 24, wherein the exhaust gas that has passed through the heat exchanger is introduced into the processing unit through the object introduction unit. 26. A processing device for a gas, a processing device for a solid,
The apparatus further includes a separation device for separating gas and solid in the processing object including gas and solid, and the substantially gas processing object obtained by the separation by the separation device is provided in the object introduction unit. 3. A substantially solid object to be processed, which is introduced into a gas processing device through a separation device and obtained by separation by the separation device, is introduced into the solid processing device through an object introduction portion. 23. The apparatus for treating an organic chlorine compound according to any one of claims to 22. 27. An incinerator as a source of an object to be treated, and an apparatus for heating a substance to be treated into a hot gas for processing,
27. The apparatus for treating an organochlorine compound according to claim 26, further comprising a heat exchanger and / or another heating device that heats the processing substance with the exhaust gas from the incinerator, wherein the exhaust gas is introduced into the separation device. 28. An apparatus for heating a processing substance into a processing hot gas by heating the processing substance by exhaust gas from an incinerator, or a heat exchanger and another heating apparatus. 28. The apparatus for treating an organochlorine compound according to claim 27, wherein the exhaust gas cooled via the heat exchanger is introduced into a separation device. 29. With the solid separated by the separation device,
28. The solid waste generated in the incinerator is introduced into the solid processing device through the object introduction part.
29. The apparatus for treating an organic chlorine compound according to 28. 30. A plurality of processors, a processor into which an object to be treated is introduced through an object introduction section, and a processor into which a processing substance is introduced through a processing substance introduction section. It is equipped with a switching device that can be sequentially switched to become one, in some processors, the target organic chlorine compound that can be contained in the processing target introduced through the target introduction part is adsorbed by the adsorbent, In all other processors or some other processors, the target organochlorine compound adsorbed by the adsorbent is dechlorinated by the processing hot gas as the processing substance introduced through the processing substance introduction section. The organic chlorine compound treatment apparatus according to any one of claims 2 to 25, which is subjected to a detoxification treatment. 31. A plurality of gas and solid processing units, or a plurality of gas and solid processing units, and a plurality of gas or solid processing units. As for the processing equipment, it is possible to sequentially switch between the processing equipment that introduces the processing target through the target introduction part and the processing equipment that introduces the processing substance through the processing substance introduction part so that both processing units are separate. Equipped with a switching device capable of, in some of the plurality of gas or solid processing units, the target organic chlorine compound that can be contained in the processing target introduced through the target introduction part is adsorbed. In all or some of the plurality of gas or solid processors that are adsorbed by the agent, the target organochlorine compound adsorbed by the adsorbent is used for processing. Substance introduction Organic chlorine compounds processing device according to any one of claims 26 to 29 is processed dechlorinated harmless by treatment for hot gas as introduced processing substance through. 32. A discharge discharged from a product discharge section of a processing device is introduced, and a solvent or a solvent mixture obtained by mixing an acid or alkali and / or an oxidizing agent or a reducing agent with a solvent is introduced into the discharge. 4. A harmful gas removing unit that removes harmful gas that may be present in the exhaust by the solvent or the solvent mixture by dispersing the harmful gas.
The apparatus for treating an organic chlorine compound according to any one of claims 1 to 7. 33. An object to be treated which can contain a target organic chlorine compound is led to an adsorbent for the target organic chlorine compound comprising zeolite, whereby the target organic chlorine compound which can be contained in the object to be treated becomes an adsorbent. The method is characterized in that the target organic chlorine compound adsorbed on the adsorbent is dechlorinated and made harmless by adsorbing and introducing an inert and / or reducing heat gas for processing as a processing substance to the adsorbent. Organic chlorine compound treatment method. 34. The method for treating an organic chlorine compound according to claim 33, wherein the target organic chlorine compound is at least one selected from the group consisting of dioxins, dioxin precursors, and PCBs. 35. The method for treating an organochlorine compound according to claim 33, wherein the treatment object having reached the adsorbent is substantially a gas. 36. The method for treating an organochlorine compound according to claim 33, wherein the treatment object having reached the adsorbent is substantially solid. 37. The method for treating an organochlorine compound according to claim 33, wherein the treatment object having reached the adsorbent is substantially composed of gas and solid. 38. The method according to claim 33, wherein at least after detecting that the adsorbent is dried to a predetermined state or more, an inert and / or reducing heat gas for treatment is introduced to the adsorbent as a treatment substance. 37. The method for treating an organochlorine compound according to any one of 37. 39. The zeolite according to claim 33, wherein the pore diameter of 50% or more of the micropores is 6 to 13 Å.
39. The method for treating an organochlorine compound according to any one of items 38 to 38. 40. The pore size of 80% or more of micropores in zeolite is 6 to 13 Å.
39. The method for treating an organochlorine compound according to any one of items 38 to 38. 41. The method according to claim 1, wherein the zeolite has a Si content in its component.
34. The compound is hydrophobic with an atomic ratio of / Al of 3 or more.
41. The method for treating an organic chlorine compound according to any one of the above items. 42. The method for treating an organochlorine compound according to claim 33, wherein the treating substance is an inert gas and / or a reducing gas. 43. The method according to claim 42, wherein the inert gas is at least one selected from the group consisting of nitrogen gas, helium gas, neon gas, argon gas, krypton gas and xenon gas. . 44. The method according to claim 42, wherein the reducing gas is a hydrogen gas and / or a carbon monoxide gas. 45. The method for treating an organochlorine compound according to claim 33, wherein the temperature of the treatment hot gas reaching the adsorbent is 150 to 600 ° C.