JP2005272635A - Method for converting sludge into fuel, thermal cracking processing method and installations therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effectively utilizing an industrial waste as an energy resource by which a cleaning treatment is safely carried out at combustion, and dispersion of calories of combustion is improved. <P>SOLUTION: An emulsion fuel is formed (S103) by mixing a material containing an organic chlorine compound with a chlorine-remover reacting with the chlorine component contained in the material to form harmless salts instead of the chlorine component, with a solid combustible component and a liquid combustible component. The emulsion fuel may be utilized as a fuel for a thermal cracking processing (S101) or a combustion treatment (S104) for burning a gas generated at the thermal cracking treatment. The solid combustible component is a powdery carbide free from water, and formed by the thermal cracking processing (S101) by indirect heating of a raw material containing an organic material. The liquid combustible component involves petroleum, heavy oil, waste oil, waste oil and fat material and a mixture thereof. A toxic substance-remover for reacting with a toxic substance component in the raw material to form the harmless salts instead of the toxic substance is properly added to and mixed with the raw material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for converting a fuel containing an organic chlorine compound into a fuel, a thermal decomposition processing method, and a facility thereof.

  In recent years, POPs harmful substances (residual organic pollutants such as aldrin, dieldrin, endrin, DDT, hebutachlor, chlordane, HCB (hexachlorobenzene), myrex, toxaphene, PCB (polychlorinated biphenyl), dioxins, etc. Various techniques for decomposing substances containing an organic chlorine compound having a melting point of 80 ° C. or higher or a boiling point of 300 ° C. or higher, such as “Persistent Organic Pollutants”) have been proposed. Specific examples of substances containing organochlorine compounds include PCB-containing oils, hazardous waste paints, waste fuels, hazardous chemicals, untreated explosives, etc. used in insulating oils for electrical equipment such as transformers and capacitors. Applicable.

  In particular, the following decomposition techniques have been proposed as means for decomposing organochlorine compounds by combustion.

  According to the organochlorine compound decomposition method disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2002-115835), an oil containing an organochlorine compound is mixed with a metal compound (such as sodium carbonate) that easily reacts with chlorine and water. The organic chlorine compound is decomposed by burning the emulsified fuel.

  According to the PCB waste oil treatment method disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2001-295635), PCB waste oil is combusted by mixing and combusting PCB waste oil, heavy oil, and water.

  According to the method for detoxifying a PCB-containing material disclosed in Patent Document 3 (Japanese Patent Application Laid-Open No. 2002-147722), the PCB-containing material and heavy oil are mixed and burned to decompose the PCB and harm the PCB-containing material. Processing is being performed.

  According to the combustion decomposition method and high temperature incinerator of PCB disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 2002-267135), the PCB is decomposed by mixing and burning the PCB, the liquid hydrocarbon and the reducing water. Yes.

  Patent Document 5 (Japanese Patent Application Laid-Open No. 2003-155487) discloses a method for producing an oil-in-water type emulsion fuel, which is not a PCB-containing material, but is prepared by mixing water, oil and a surfactant. Have gained.

  On the other hand, the following techniques are known as techniques for using a flammable solid (such as carbide) as an emulsion fuel.

  According to the method for producing a liquid carbon fuel disclosed in Patent Document 6 (Japanese Patent Application Laid-Open No. 2001-348582), the average particle size of the carbide obtained by carbonizing the combustible waste obtained by separating the general waste is obtained in water. By pulverizing to 100 μm or less, pulverized coal is obtained, from which salt and heavy metals are removed, dehydrated to reduce the water content, and oil is mixed to obtain fuel.

  According to the method for producing a liquid carbon fuel disclosed in Patent Document 7 (Japanese Patent Laid-Open No. 10-130663), an organic substance is thermally decomposed by low-temperature indirect heating in an oxygen-free closed sealed atmosphere to produce a carbon material. Liquid carbon fuel is manufactured by pulverizing a raw material and mixing predetermined water with this powdery carbon raw material.

  According to the liquefied fuel generation system disclosed in Patent Document 8 (Japanese Patent Application Laid-Open No. 11-349966), a powder fluid obtained by crushing and adjusting moisture to discharge combustible materials such as general waste and industrial waste waste to form a waste slurry. Further, the combustible material is liquefied by mixing the oil and the surfactant.

According to the hydrofuel combustion method disclosed in Patent Document 9 (Japanese Patent Laid-Open No. 2002-89832), a liquefied fuel is obtained by mixing water and oil.
JP 2002-115835 A JP 2001-295635 A JP 2002-147722 A JP 2002-267135 A JP 2003-155487 A JP 2001-348582 A JP-A-10-130663 Japanese Patent Laid-Open No. 11-349966 JP 2002-89832 A

  Substances containing organochlorine compounds such as PCB-containing oils have various PCB concentrations (several tens of ppm to 100%) and various PCB structures, resulting in large variations in the amount of combustion heat. Therefore, in the treatment method according to Patent Document 1, although a certain degree of dechlorination effect is obtained, there is a variation in the amount of combustion heat, so that an incompletely combusted organochlorine compound may remain. Moreover, in the processing methods according to Patent Documents 1, 2, 4, and 5 to 9, since water is mixed, the combustion efficiency is lowered. Furthermore, in the processing methods according to Patent Documents 2 to 9, there is a risk that POP-based harmful substances such as PCB and dioxins remain in the gas and dust generated during combustion. These problems are not limited to PCB-containing oils used in insulating oils for electrical equipment such as transformers and capacitors, but organics with different concentrations such as hazardous waste paint, waste fuel, hazardous chemicals, untreated explosives, etc. It can happen in the same way when processing chlorine-containing oil. On the other hand, since these organic chlorine-containing substances are rich in carbon and hydrogen components, they are potentially useful as energy resources such as fuel.

  The present invention has been made in view of such circumstances, and a substance containing an organic chlorine compound is used as a constituent material of a fuel, and combustion is performed by mixing a chlorine removing agent, a solid combustible component, and a liquid combustible component with the material. The present invention is to provide a method of fuel conversion and pyrolysis processing of a material containing an organochlorine compound that can be safely purified at times and can improve the variation in combustion heat quantity and effectively use industrial waste as an energy resource, and a facility thereof.

  Therefore, the method of fueling a substance containing an organochlorine compound of the present invention includes a substance containing a method organochlorine compound, and a chlorine removing agent that reacts with a chlorine component contained in this substance to produce a harmless salt. A solid combustible component and a liquid combustible component are mixed to produce an emulsion fuel.

  Further, the pyrolysis processing method of the present invention includes a step of pyrolyzing a raw material to produce a powdered carbide, a step of combusting a gas generated from the raw material by the pyrolysis treatment, and an organic chlorine compound A chlorine-containing agent that reacts with a chlorine component contained in the substance to produce a harmless salt, and a part of the generated carbide as a solid combustible component, and a liquid combustible component. Producing emulsion fuel, and the emulsion fuel is used as fuel for the thermal decomposition treatment or fuel treatment.

  Furthermore, the thermal decomposition processing facility of the present invention includes an indirect heating means including a rotary furnace that generates a powdered carbide by thermally decomposing the raw material by conveying and stirring and heating, and for heating the rotary furnace. A heat source that generates heat, a gas combustion means for burning the gas generated from the raw material by the heating, a substance containing an organochlorine compound, and a chlorine component contained in this substance reacts to produce harmless salts. And a fuelizing means for producing an emulsion fuel by mixing a part of the generated carbide as a solid combustible component and a liquid combustible component, and supplying the emulsion fuel to the heating source or the gas It is used as fuel for combustion means.

  Further, as another pyrolysis processing facility, an indirect heating means including a rotary furnace for generating a powdered carbide by thermally decomposing the raw material by conveying and stirring and heating, and a gas generated from the raw material by the heating A gas combustion means for combusting, a substance containing an organochlorine compound, a chlorine removing agent that reacts with a chlorine component contained in this substance to produce a harmless salt, and a solid combustible component. A fueling means for mixing the liquid combustible component with the liquid combustible component to produce an emulsion fuel, using the emulsion fuel as a fuel for the gas combustion means, and using the hot gas obtained by the gas combustion means as the fuel It is used to heat the rotary furnace.

  In these pyrolysis processing facilities, when supplying the raw material to the indirect heating means, a harmful substance removing agent supply means for adding a harmful substance removing agent that reacts with the harmful substance component to produce a harmless salt is generated in the raw material. I have.

  In the fuel conversion method and pyrolysis processing method of the substance containing the organic chlorine compound and its facility, the organic chlorine compound includes a residual organic organic pollutant, specifically, PCB-containing oil, aldrin, dieldrin And oil containing endrin, DDT, hebutachlor, chlordane, HCB (hexachlorobenzene), myrex, toxaphene, dioxins and the like. The liquid combustible component includes a liquid substance containing a hydrocarbon component, and specifically includes any one of petroleum, heavy oil, waste oil, waste oil and fat substances, or a mixture thereof.

  As the dechlorinating agent, at least one selected from alkali metals, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds or a mixture of two or more types is effective.

  Examples of the alkali metal compound include oxides such as lithium, sodium, potassium, rubidium, and cesium, hydroxides, bicarbonates, carbonates, silicates, phosphates, aluminates, nitrates, sulfates, and the like. Specifically, for example, sodium hydrogen carbonate, sodium sesquicarbonate, sodium carbonate, natural soda, potassium carbonate, potassium hydrogen carbonate, sodium potassium carbonate, sodium hydroxide, potassium hydroxide and the like can be mentioned.

  Examples of the alkaline earth metal compound include calcium, magnesium, strontium, barium oxides, hydroxides, bicarbonates, carbonates, and specific examples include lime, slaked lime, calcium carbonate, dolomite, and the like. Is mentioned.

  According to the method for fuelizing a substance containing an organic chlorine compound according to the present invention, an organic chlorine compound-containing substance is used as a constituent substance, and a solid combustible component, a liquid combustible component, and a chlorine removing agent are mixed with the emulsion fuel. Therefore, stable combustion can be continued, and at the time of combustion, the chlorine remover reacts with the chlorine component of the organic chlorine compound to produce harmless salts, so that PCBs and dioxins can be contained in exhaust gas and dust. It is extremely suppressed that POP-based harmful substances such as these remain. Therefore, the fuel obtained by the fueling method of the present invention can be safely purified and has improved variations in the amount of combustion heat. As a result, industrial waste can be effectively used as an energy resource.

  Further, according to the pyrolysis processing method using the fuel of the present invention and the facility capable of performing safe and stable combustion, hot air having a stable temperature can be obtained. Heating can be performed correctly according to the set value, and stable carbide processing can be realized. As a result, the running cost of the pyrolysis processing facility can be reduced, and an energy utilization system that can be used by processing various starting materials into carbides without being discarded can be constructed.

  Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic explanatory view of a process for converting an organic chlorine compound into fuel and pyrolysis according to the present invention. The organic chlorine compound fueling method and pyrolysis processing method of the present invention, and these facilities are used to remove chlorine produced by substitution with a substance containing an organic chlorine compound and a harmless salt by reacting with a chlorine component contained in the substance. The emulsion fuel is generated by mixing the agent, the solid combustible component, and the liquid combustible component (S103).

  The organic chlorine-containing substance includes oil containing persistent organic pollutants, such as PCB, aldrin, dieldrin, endrin, DDT, hebutachlor, chlordane, HCB, myrex, toxaphene, dioxins and the like. Examples thereof include oil and insulating oil.

  As the chlorine removing agent, at least one selected from alkali metals, alkali metal compounds, alkaline earth metals, and alkaline earth metal compounds may be used, or a powdery material in which two or more types are mixed may be used. In this way, by reacting with harmful substance components in the raw material such as chlorine remover and burning it with harmful substance remover chemicals that are produced by substitution with harmless salts, it is brought into contact with chlorine of PCBs and harmless salts during combustion. Therefore, it is extremely suppressed that POP harmful substances such as PCBs and dioxins remain in the exhaust gas and dust.

  The solid combustible component is a powdered carbide that does not contain moisture, and is generated by pyrolyzing (S101) a raw material containing an organic substance by indirect heating. In addition, since the raw materials may contain harmful chlorine components, dioxins, environmental hormones, etc., they generate carbides that do not leave harmful substances by thermal decomposition by indirect heating in a low oxygen atmosphere. ing. Here, the chlorine component and dioxins are left in the carbide by carrying out thermal decomposition together with the harmful substance removing agent agent that reacts with the harmful substance component in the raw material such as the chlorine removing agent to produce a harmless salt. It is preventing.

  The carbide should have a smaller diameter. For example, if it is 1 mm or less, it may be used as it is, but it may be appropriately pulverized in consideration of the diameter of the tip of the burner provided in the combustion means using the emulsion fuel ( S102). Examples of the pulverizing means include a pulverizer such as a jet mill capable of obtaining a fine powder of a micron unit. Further, the grinding of the carbide is dry, and in the case of wet, a drying step is required.

  Examples of the liquid combustible component include a liquid substance containing a hydrocarbon component. For example, various waste oils, oils and fats generated in various product production processes (for example, during production of edible oil, etc.) may be used. Examples of the oils include liquid combustibles such as petroleum and heavy oil. Examples of the waste oil include recovered waste oil and waste oil after the production of processed foods. An emulsion state is maintained in these liquid fuels by adding an emulsifier (surfactant) as necessary.

  The emulsion fuel is used as a fuel for various purposes. For example, the emulsion fuel is used as a fuel in the pyrolysis process (S101) or a combustion process step (S104) for burning the gas generated by the pyrolysis process, thereby converting the organic material into a fuel. The running cost is reduced.

  In using the emulsion fuel, a heating source (not shown) provided in S101 (for example, the hot air furnace 27 shown in FIG. 2) or the gas combustion furnace 3 provided in S104 is supplied with emulsion fuel and compressed air. A two-fluid burner 30 that can be supplied may be provided. The two-fluid barter 30 may be a known one as long as it can introduce and supply two different fluids. For example, there are two-fluid burners disclosed in JP2002-130673, JP2002-053877, JP2001153307, JP10-227432, JP07-268238, and the like. Can be mentioned.

  The hot air generated in the gas fuel furnace 3 may be used as a heat source for heating a boiler or the like in addition to drying of raw materials or pyrolysis processing. At this time, it is better to remove the ash contained in the hot air by the hot cyclone 31. Since it is after combustion, the exhaust gas temperature is high and a cyclone rich in heat resistance is suitable. Metals that do not burn can be recovered with this cyclone. The hot cyclone 31 may be a known one that is used as a dust removing means. For example, JP 2003-294217 A, JP 2002-309262 A, JP 2002-295820 A, and JP 2002-295819 A. JP-A-2002-286216, 2001-31588, JP-A-05-125420, and the like.

  As described above, an organic fuel compound-containing material, a solid combustible component, a liquid combustible component, and a chlorine removing agent are mixed to obtain an emulsion fuel by fueling and pyrolyzing the organic material of the present embodiment. In this way, stable combustion is continued. In addition, since a chlorine removing agent is added and mixed, it reacts with the chlorine component of the organochlorine compound during combustion to produce a non-hazardous salt, and the residual of PCB, dioxins, etc. in the exhaust gas and dust is extremely suppressed. The Therefore, hot air having a stable temperature can be obtained, and an object to be heated (such as a rotary furnace) can be heated correctly according to the set value, so that stable production and production of carbide can be achieved. In addition, by using a substance containing an organic chlorine compound as a fuel constituent and adding and mixing a chlorine remover, it can be safely purified, and liquid flammable components are mixed, thus improving the variation in combustion heat. . By using the obtained emulsion fuel, the running cost of the pyrolysis processing facility is reduced, and an energy utilization system that can be used by processing various starting materials into carbides without discarding them is realized.

  FIG. 2 is a schematic configuration diagram showing an embodiment of the thermal decomposition processing facility of the present invention.

  The heat processing facility of the present embodiment is a heat processing facility in which raw materials are pyrolyzed by indirect heating to obtain carbides, and includes the fuelizing means 1 and the gas combustion furnace 3 described with reference to FIG.

  The heating furnace 2 indirectly heats and drys the raw material at 350 to 450 ° C. under a constant residence time, or indirectly heats the dried raw material at 450 to 600 ° C. under a constant residence time. Indirect heating means for carbonizing. Although the heating furnace 2 of this embodiment is a form example in the case where drying and carbonization are performed in a single furnace, a plurality of heating furnaces 2 may be provided to perform drying and carbonization individually.

  The heating furnace 2 adopts a rotary kiln system, and external heating means (heating jacket 21) that heats the rotary furnace 20 from the outside by circulating hot air gas around the rotary furnace 20 to the rotary furnace 20 into which raw materials are introduced. Is attached. Hot air gas is introduced from the hot air furnace 27. The rotary furnace 20 has a cylindrical shape, is supported by a plurality of support rollers 22, and is rotated by a rotating means 23 having a rotation drive source. At this time, a plurality of feed blades (not shown) for stirring and conveying the introduced raw material may be provided inside the rotary furnace 20.

  On one end side of the rotary furnace 20, a duct 24 is connected to the rotary furnace 20 through a seal member 240 in a freely and airtight manner. A guide plate 241 for guiding the raw material into the rotary furnace 20 is provided in the duct 24. The duct 24 is connected to raw material supply means (not shown) such as a hopper facility for carrying the raw material. At this time, the raw material supply means is provided with a weighing device for supplying the raw material, and the heat treatment is stabilized by supplying the raw material more quantitatively.

  On the other end side of the rotary furnace 20, a duct 25 for discharging dry matter or carbide generated in the rotary furnace 20 is connected to the rotary furnace 20 through a seal member 250 in a freely and airtight manner. The duct 25 is connected to a pipe 251 for sucking and discharging water vapor and pyrolysis gas generated in the rotary furnace 20. The pipe 251 may be provided with an ejector for forcibly supplying the water vapor or pyrolysis gas to the gas combustion furnace 3 by the gas sucked by the blower 26. When the carbide is recovered, it is supplied to the fueling means 1 (line (A)) or used for various uses such as an adsorbent and a soil conditioner.

  The hot air furnace 27 is an indirect heating source that supplies hot air gas, and includes a combustion burner for generating hot air gas that is a heating medium of the rotary furnace 20. The hot air gas generated in the hot air furnace 27 is supplied into the heating jacket 21 of the heating furnace 1 to heat the rotary furnace 20. At this time, temperature adjusting air is appropriately injected into the hot air gas, and the gas temperature is adjusted (for example, 300 to 700 ° C.). The heating medium (hot air gas) discharged from the heating jacket 21 is exhausted. Further, a part of the heating medium is used as an ejector driving gas in the gas combustion furnace 3 or reused as a hot air gas supplied to the heating jacket 21 by the blower. In the hot stove 27, when the emulsion fuel obtained by the fueling means 1 is used as a fuel, the combustion burner may adopt a two-fluid burner structure.

  The gas combustion furnace 3 uses the emulsion fuel generated by the fueling means 1 and converts the steam and pyrolysis gas introduced from the heating furnace 2 under a certain atmosphere and residence time (for example, an atmosphere of 800 ° C. or higher). More specifically, for example, a combustion means for detoxifying by burning in an atmosphere of about 850 ° C. for a residence time of 2 seconds or more). Air is appropriately introduced into the gas to be treated from outside the system to assist combustion. The gas combustion furnace 3 includes a gas combustion chamber to which a gas to be processed is supplied, and includes a two-fluid burner for introducing compressed air and emulsion fuel. Combustion by the two-fluid burner is appropriately controlled by adjusting the amount of fuel supplied. The gas burned in the gas combustion furnace 3 is sucked into the blower 6 and exhausted after passing through the heat exchanger 4 and the bag filter 5. When the hot air generated in the gas combustion furnace 3 is used as a heating source in the heating furnace 2, it is not necessary to provide the hot air furnace 27.

  The heat exchanger 4 cools the gas to about 200 to 150 ° C. by a gas-gas heat exchange system using air as a cooling medium. At this time, fresh air not containing at least a sulfur component is appropriately supplied to the gas to be cooled (combusted gas), and the gas temperature is adjusted appropriately. The cooled gas is further supplied to the bag filter 5 and subjected to dust removal treatment, and then discharged out of the system. On the other hand, the air heated by heat exchange may be used for generating hot air gas in the hot air furnace 27.

Schematic explanatory diagram of organic substance fueling and pyrolysis process according to the present invention The schematic block diagram which showed the example of embodiment of the thermal decomposition processing facility which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Fueling means 2 ... Heating furnace 3 ... Gas combustion furnace, 30 ... Two fluid burner, 31 ... Hot cyclone 4 ... Heat exchanger 5 ... Bag filter 6 ... Blower

Claims (9)

  Emulsion fuel is produced by mixing a substance containing an organic chlorine compound, a chlorine remover that reacts with the chlorine component contained in this substance and generates a harmless salt, a solid combustible component, and a liquid combustible component. A method for converting a material containing an organic chlorine compound into a fuel. 2. The method for fuelizing a substance containing an organic chlorine compound according to claim 1, wherein the organic chlorine compound is a persistent organic organic pollutant. 3. The method for fuelizing a substance containing an organic chlorine compound according to claim 2, wherein the residual organic organic pollutant is a PCB-containing oil. The method for fuelizing a substance containing an organic chlorine compound according to any one of claims 1 to 3, wherein the solid combustible component is a powdered carbide. The liquid combustible component is any one of petroleum, heavy oil, waste oil, waste oil and fat substance, or a mixture thereof, wherein the organic chlorine compound-containing substance according to any one of claims 1 to 4 is used. Fueling method. A process of pyrolyzing the raw material to produce powdered carbide,
A step of combusting the gas generated from the raw material by the pyrolysis treatment;
A substance containing an organic chlorine compound, a chlorine removing agent that reacts with a chlorine component contained in the substance to produce a harmless salt, a part of the generated carbide as a solid combustible component, a liquid combustible component, Mixing emulsions to produce emulsion fuel,
A thermal decomposition processing method, wherein the emulsion fuel is used as a fuel for the thermal decomposition treatment or fuel treatment. An indirect heating means equipped with a rotary furnace for generating a powdered carbide by thermally decomposing the raw material by conveying and stirring and heating;
A heating source for generating heat for heating the rotary furnace;
Gas combustion means for burning gas generated from the raw material by the heating;
A substance containing an organic chlorine compound, a chlorine removing agent that reacts with a chlorine component contained in the substance to produce a harmless salt, a part of the generated carbide as a solid combustible component, a liquid combustible component, And a fuelizing means for producing emulsion fuel by mixing
A thermal decomposition processing facility using the emulsion fuel as a fuel for the heating source or the gas combustion means. An indirect heating means equipped with a rotary furnace for generating a powdered carbide by thermally decomposing the raw material by conveying and stirring and heating;
Gas combustion means for burning gas generated from the raw material by the heating;
A substance containing an organic chlorine compound, a chlorine removing agent that reacts with a chlorine component contained in the substance to produce a harmless salt, a part of the generated carbide as a solid combustible component, a liquid combustible component, And a fuelizing means for producing emulsion fuel by mixing
Utilizing the emulsion fuel as fuel for the gas combustion means A thermal decomposition processing facility characterized in that the hot gas obtained by the gas combustion means is used for heating the rotary furnace. A toxic substance removing agent supply means for adding a toxic substance removing agent that reacts with a toxic substance component to produce a non-toxic salt when the raw material is supplied to the indirect heating means. Pyrolysis processing facility according to 7 or 8.

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