EP0860183A2 - Verfahren und Mittel zur Entfernung von Schadstoffen - Google Patents

Verfahren und Mittel zur Entfernung von Schadstoffen Download PDF

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Publication number
EP0860183A2
EP0860183A2 EP98102829A EP98102829A EP0860183A2 EP 0860183 A2 EP0860183 A2 EP 0860183A2 EP 98102829 A EP98102829 A EP 98102829A EP 98102829 A EP98102829 A EP 98102829A EP 0860183 A2 EP0860183 A2 EP 0860183A2
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EP
European Patent Office
Prior art keywords
chlorine
removal agent
carbonate
treatable material
alkali metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98102829A
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English (en)
French (fr)
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EP0860183A3 (de
EP0860183B1 (de
Inventor
Yoshiyuki Kashiwagi
Haruhisa Ishigaki
Nobuyuki Yoshioka
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Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
Original Assignee
Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
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Publication date
Priority claimed from JP9038729A external-priority patent/JPH10235149A/ja
Priority claimed from JP9038726A external-priority patent/JPH10235147A/ja
Priority claimed from JP9038737A external-priority patent/JPH10235311A/ja
Priority claimed from JP9038728A external-priority patent/JPH10235148A/ja
Priority claimed from JP9160911A external-priority patent/JPH119938A/ja
Priority claimed from JP9160914A external-priority patent/JPH119939A/ja
Priority claimed from JP9265993A external-priority patent/JPH11101417A/ja
Application filed by Meidensha Corp, Meidensha Electric Manufacturing Co Ltd filed Critical Meidensha Corp
Publication of EP0860183A2 publication Critical patent/EP0860183A2/de
Publication of EP0860183A3 publication Critical patent/EP0860183A3/de
Publication of EP0860183B1 publication Critical patent/EP0860183B1/de
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F23G5/0276—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using direct heating
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

  • This invention relates to improvements in a process for removing a noxious component (such as chlorine and/or sulfur) from a material (referred to as "treatable material") containing chlorine and or sulfur, such as urban waste or trash and industrial waste, and to improvements in a noxious component removal agent to be used in the process, and more particularly to a technique in which the noxious component removal agent is reacted with noxious component-containing gas (hydrogen chloride, chlorine gas and/or sulfur oxide gas) generated upon thermal treatment of the trash and waste to form harmless gas and compounds.
  • noxious component-containing gas hydrogen chloride, chlorine gas and/or sulfur oxide gas
  • Such urban waste includes waste or trash from general homes and offices and therefore is mainly constituted of combustible waste.
  • This combustible waste includes a variety of chemical substances (for example, plastic) containing a large amount of polyvinyl chloride, and a variety of materials (for example, paper used in offices) containing a large amount of chlorine components such as chlorine-containing bleaching agent.
  • incineration has been usually employed for treating such waste.
  • chlorine-containing gas such as hydrogen chloride gas and chlorine gas is generated thereby raising problems of environmental pollution and deterioration of incinerating facility under the action of the chlorine-containing gas.
  • a chlorine removal agent such as slaked lime, calcium carbonate or the like as disclosed, for example, in Japanese Patent Publication No. 2-10341.
  • chlorine-containing substances such as chloride and other chlorine compounds are problematic, in which chlorine-containing gas generated in the course of incineration damages the incinerator itself and corrodes steam pipes and further leads to problems of producing dioxin which is virulently poisonous. Accordingly, chlorine-containing gas has been usually reacted with slaked lime or the like in the bag filter thereby being prevented from being emitted to the atmospheric air. Such measures can be expected to obtain a certain effect under treatment of burnt gas so that chlorine-containing gas can be prevented from being dispersed to the atmospheric air. However, it is difficult to completely remove chlorine-containing substances by such measures because chlorine-containing substances remain in a residue formed after incineration of the treatable material. This forms part of cause of generating dioxin. Even by the measure of adding slaked lime or calcium carbonate during the incineration, chlorine-containing gas has not been able to be sufficiently prevented from its generation.
  • alkali material is sprayed into the incinerator in which the treatable material is incinerated as disclosed, for example, in Japanese Patent Provisional Publication No. 54-93864.
  • chlorine-containing gas which has been once generated and filled in the incinerator is treated, which is similar to the above measure and therefore renders it impossible to completely remove chlorine-containing gas.
  • incineration of the treatable material is accomplished upon adding thereto alkali material containing calcium such as lime (CaCO 3 ), slaked lime (Ca(OH) 2 ) or the like, or that SOx is passed through a filter filled with the alkali material to remove SOx as disclosed, for example, in Japanese Patent Publication No. 2-10341, Japanese Patent Provisional Publication No. 1-296007, and Japanese Patent Provisional Publication No. 59-12733. Reactions made in these propositions are as follows:
  • Japanese Patent Provisional Publication No. 5-33916 discloses spraying alkali material such as slaked lime into a furnace; however, no sufficient effect of removing chlorine-containing gas can be expected because the alkali material is brought into contact with chlorine-containing gas which has been once generated and filled in the furnace.
  • the inventors of the present invention have found that the noxious chlorine-containing substances or gases can be effectively reacted with alkali metal compound (particularly alkali metal carbonate, alkali metal hydrogen carbonate and alkali metal hydroxide) so that the noxious chlorine-containing gases are effectively converted into harmless chlorides. Additionally, it has been confirmed that alkali metal component is also effective for converting noxious sulfur-containing gases into harmless sulfite.
  • alkali metal compound particularly alkali metal carbonate, alkali metal hydrogen carbonate and alkali metal hydroxide
  • the present invention has been envisaged depending upon the above knowledge and to provide an improved noxious component removal process using a particular noxious component removal agent containing alkali metal compound, in which noxious component-containing gases generated upon heating the treatable material are immediately reacted with the noxious removal agent thereby to form harmless compound, preventing emission of noxious component-containing gas into the atmospheric air.
  • Another object of the present invention is to provide an improved noxious component removal process to be applied in a thermal treatment process for a waste or treatable material, by which generally no noxious component-containing gas is contained in emitted gas and also in a residue formed upon the thermal treatment of the treatable material, thereby generally completely preventing noxious substances (including dioxin) from being generated in the thermal treatment process.
  • Another object of the present invention is to provide an improved noxious component removal process in which noxious component-containing gas generated upon thermal treatment of a waste or treatable material can be generally completely removed during the thermal treatment thereby omitting the possibility of generating noxious substances (including dioxin), while a residue contains only harmless compound without containing noxious component-containing substances.
  • a further object of the present invention is to provide an improved noxious removal agent which is high in effect for removing noxious component-containing substances or gases and to be used at any steps in a noxious component removal process in which a waste or treatable material is thermally treated.
  • a first aspect of the present invention resides in a process for removing a noxious component from a treatable material containing the noxious component, comprising the following steps in the sequence set forth: (a) mixing the treatable material and a noxious component removal agent to form a mixture, the noxious component removal agent containing an alkali metal compound; and (b) heating the mixture to thermally decompose the treatable material to generate a noxious component-containing substance and cause the noxious component-containing substance to contact and react with the noxious component removal agent to form a harmless compound.
  • a second aspect of the present invention resides in a process for removing at least one of chlorine and sulfur from a treatable material containing at least one of chlorine and sulfur, comprising the following steps in the sequence set forth: (a) mixing the treatable material and a chlorine and sulfur removal agent to form a mixture, the chlorine and sulfur removal agent containing an alkali metal compound; and (b) heating the mixture to thermally decompose the treatable material to generate at least one of a chlorine-containing substance and a sulfur-containing substance and cause at least one of the chlorine-containing substance and the sulfur-containing substance to contact and react with the chlorine and sulfur removal agent to form at least one of harmless chloride and sulfite.
  • a third aspect of the present invention resides in a process for removing chlorine from a treatable material containing chlorine, comprising the following steps in the sequence set forth: (a) mixing the treatable material and a chlorine removal agent to form a mixture, the chlorine removal agent containing an alkali metal compound; and (b) heating the mixture to thermally decompose the treatable material to generate a chlorine-containing substance and cause the chlorine-containing substance to contact and react with the chlorine removal agent to form a harmless chloride.
  • a fourth aspect of the present invention resides in a noxious component removal agent to be used in a process for removing noxious component from a treatable material containing the noxious component, the chlorine removal agent containing an alkali metal compound, the noxious removal agent being contactable and able to react with a noxious component-containing substance generated from the treatable material upon heating the treatable material, so as to form a harmless compound.
  • a fifth aspect of the present invention resides in a chlorine and sulfur removal agent to be used in a process for removing at least one of chlorine and sulfur from a treatable material containing at least one of chlorine and sulfur, the chlorine and sulfur removal agent containing an alkali metal compound, the chlorine and sulfur removal agent being contactable and able to react with at least one of a chlorine-containing substance and a sulfur-containing substance generated from the treatable material upon heating the treatable material, so as to form at least one of harmless chloride and sulfite.
  • a sixth aspect of the present invention resides in a chlorine removal agent to be used in a process for removing chlorine from a treatable material containing chlorine, the chlorine removal agent containing an alkali metal compound, the chlorine removal agent being contactable and able to react with a chlorine-containing substance generated from the treatable material upon heating the treatable material, so as to form a harmless chloride.
  • a seventh aspect of the present invention resides in a chlorine removal agent to be used in a process for removing at least one of chlorine and sulfur from a treatable material containing at least one of chlorine and sulfur, comprising the following steps in the sequence set forth: mixing the treatable material and a chlorine and sulfur removal agent to form a mixture, the chlorine and sulfur removal agent containing an alkali metal compound; and heating the mixture to thermally decompose the treatable material to generate at least one of a chlorine-containing substance and a sulfur-containing substance and cause at least one of the chlorine-containing substance and the sulfur-containing substance to contact and react with the chlorine and sulfur removal agent to form at least one of harmless chloride and sulfite, wherein the chlorine removal agent contains an alkali metal compound.
  • An eighth aspect of the present invention resides in a system for removing at least one of chlorine and sulfur from a treatable material containing at least one of chlorine and sulfur, comprising: a device for mixing the treatable material and a chlorine and sulfur removal agent to form a mixture, the chlorine and sulfur removal agent containing an alkali metal compound; a furnace into which the mixture of the treatable material and the chlorine and sulfur removal agent is supplied, the furnace being adapted to form therein a low oxygen concentration atmosphere; and a heating device for heating the mixture in the low oxygen concentration atmosphere in the furnace to thermally decompose the treatable material so as to accomplish dry distillation of the treatable material, in which the mixture generates at least one of a chlorine-containing substance and a sulfur-containing substance and cause at least one of the chlorine-containing substance and the sulfur-containing substance to contact and react with the chlorine and sulfur removal agent to form at least one of harmless chloride and sulfite.
  • the noxious component (such as chlorine and/or sulfur) removal process of the present invention no generation of noxious component-containing gas is made throughout whole steps in a thermal treatment process of the treatable material and throughout whole temperature ranges in the thermal treatment process, which has not been achieved by conventional noxious component removal processes which use slaked lime or calcium carbonate as the chlorine removal agent. Additionally, the residue formed upon thermal treatment of the treatable material contains no noxious component-containing substances, containing harmless compound (such as chloride and/or sulfite). Thus, the noxious component removal process of the present invention exhibits a high noxious component removal effect particularly for the treatable material containing a large amount of noxious component-containing substances or compounds of the noxious component , such as urban waste or trash.
  • the noxious component removal agent of the present invention is mixed with the treatable material so as to immediately react with noxious component-containing gas generated upon heating the treatable material, thereby to form harmless gas and compound of the noxious component.
  • the noxious component removal agent itself can be used at any steps other than a heating step for thermally decomposing the treatable material, in the course of a thermal treatment for the treatable material regardless of whether the noxious component removal agent is used at the heating step or not.
  • the noxious component removal agent itself can be used as it is even after the heating step and even in a flue, a variety of facilities for treating emitted gas, and other various conventional facilities such as an incinerator and the like. It will be understood that the noxious component (chlorine) removal agent itself of the present invention may be employed at any steps in a conventional noxious component (chlorine) removal process and in a conventional incinerating process for wastes.
  • noxious component-containing gas can be generally completely removed in the furnace for thermal treatment of the treatable material
  • a thermal treatment furnace including an incinerator
  • steam pipes and the like can be effectively prevented from being corroded, thereby prolonging life of the furnaces and the facilities.
  • the residue formed upon heating the treatable material do not contain dioxin which is virulently poisonous for human body, thus largely improving safety from the circumferential and treatment-operational viewpoints.
  • emitted gas from the furnace is harmless and combustible, and therefore the emitted gas may be reusable as fuel for a gas engine, a turbine, a boiler, a heat source of a water heating device, and fuel for a heater.
  • massed carbon components in the residue may be used as fuel, and inorganic materials in the residue may be reusable as the material of glass or cement. It will be appreciated that the noxious component removal process of the present invention cannot be affected even if the waste or treatable material contains water. No noxious chlorine-containing gas exists in emitted gas from the furnace, and therefore the emitted gas may be further heated to make a secondary combustion as a post-treatment for the emitted gas, as occasion demands.
  • Fig. 1 is a block diagram of a chlorine and sulfur removal system for carrying out the fifth embodiment of the noxious component removal process according to the present invention.
  • a process for removing noxious component (such as chlorine and/or sulfur) from a treatable material (such as urban waste or trash, or industrial waste) containing the noxious component comprises the following steps in the sequence set forth: (a) mixing the treatable material and a noxious component (chloride and/or sulfur) removal agent to form a mixture, the noxious removal agent containing an alkali metal compound; and (b) heating the mixture to thermally decompose the treatable material to generate a noxious component (chlorine and/or sulfur)-containing substance and cause the noxious component-containing substance to contact and react with the noxious component removal agent to form a harmless compound.
  • noxious component such as chlorine and/or sulfur
  • Examples of the harmful component (chlorine and/or sulfur) removal agent to be used in the above noxious component removal process are:
  • the noxious component removal agent contains at least one of sodium hydrogen carbonate, sodium carbonate, sodium sesqui carbonate, natural soda, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide (RbOH), and cesium hydroxide (CsOH), potassium carbonate, potassium hydrogen carbonate, and potassium sodium carbonate, and the like.
  • the amount of the noxious component removal agent to be used is usually within a range of from 0.05 to 10 % by weight relative to the treatable material at a starting time which is before a time at which the treatable material is mixed with the noxious component removal agent.
  • the treatable material including substances or compounds containing a large amount of chlorine component, such as polyvinyl chloride, polyvinylidene chloride, other chlorine-containing synthetic resins and/or chlorine-containing rubbers
  • the amount of the noxious component removal agent to be used is within a range of from 10 to 17 % weight relative to the treatable material at the starting time.
  • the amount of the noxious component removal agent may be selected to be larger than the chemical equivalent of chlorine-containing substance or gas (a substance or gas containing chlorine) generated from the treatable material upon heating, regardless of the weight of the treatable material. Otherwise, the amount of the noxious component removal agent may be selected to suppress the emission levels of chlorine-containing gases below permissible emission standards. Also in case the treatable material includes substances or compounds containing a large amount of sulfur component, the amount of the noxious component is selected similarly to the above.
  • the noxious component removal agent is mixed with the treatable material and heated at a thermal decomposition temperature ranging from 200 to 1000 °C in a low oxygen concentration atmosphere.
  • a thermal decomposition temperature ranging from 200 to 1000 °C in a low oxygen concentration atmosphere.
  • mixing of the noxious component removal agent and the treatable material is made before heating for thermally decomposing the treatable material, i.e., before the temperature of the treatable material rises to a level at which the thermal decomposition of the treatable material occurs.
  • chlorine compounds, sulfur compounds and substances containing chlorine and/or sulfur are thermally decomposed.
  • the low oxygen concentration atmosphere means an atmosphere in which the concentration of oxygen is low, which can be accomplished by closing the inlet and outlet of a thermal treatment furnace or tank such as a heating furnace, upon casting the mixture of the treatable material and the noxious component removal agent into the furnace. It will be understood that the low oxygen concentration atmosphere corresponds to a condition in which atmospheric air remains within the furnace whose inlet and outlet have been closed. In other words, the low oxygen concentration atmosphere corresponds to a condition in which the mixture is put in the furnace which is substantially sealed so as to prevent fresh air from being supplied into the furnace, in which a pressure in the furnace leaks out of the furnace.
  • the low oxygen concentration atmosphere does not require a complete closing or sealing state of the furnace and includes also a condition in which the side of the inlet of the furnace is closed with the treatable material itself, in which a gas pressure within the furnace is raised under heating so that supply of air from the outside of the furnace is hardly made.
  • the low oxygen concentration atmosphere may be a thermal decomposition atmosphere in which the treatable material thermally decomposes to generate so-called thermal decomposition gas of the treatable material.
  • the low oxygen concentration atmosphere accomplishes dry distillation of the treatable material.
  • the noxious component removal agent is basically mixed with the treatable material upon being cast or sprayed onto the treatable material in the furnace.
  • the noxious component removal agent may be additionally cast or sprayed onto the mixture of the treatable material and the noxious component removal agent in the furnace.
  • noxious component removal agent has been described as being mixed with the treatable material before heating or thermal decomposition of the treatable material, it will be understood that noxious component removal agent may be also effective for removing chlorine even upon contacting with dry distillation gas or emitted gas (gas generated under dry distillation of the treatable material) discharged from the furnace after heating or thermal decomposition of the treatable material. It will be also understood that the noxious component removal material may be supplied or sprayed onto the treatable material which is thermally decomposing.
  • the noxious component removal agent according to the present invention may be used to be brought into contact with chlorine-containing substance and/or sulfur-containing substance which are in any step of a noxious component removal process other than the process according to the present invention, for the purpose of removing chlorine from noxious gas or a material containing chlorine.
  • the noxious component or chlorine removal agent contains alkali metal hydrogen carbonate and/or alkali metal carbonate, i.e., at least one of sodium hydrogen carbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O).
  • alkali metal hydrogen carbonate and/or alkali metal carbonate i.e., at least one of sodium hydrogen carbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O).
  • sodium hydrogen carbonate (NaHCO 3 ) is used as the chlorine removal agent, in which the sodium hydrogen carbonate is mixed with the treatable material and heated thereby bringing about the following reaction with hydrogen chloride (HCl) which is a major chlorine-containing compound contained in gases generated from the treatable material upon heating.
  • HCl hydrogen chloride
  • alkali metal carbonate and/or alkali metal hydrogen carbonate are added to and mixed with the treatable material as the chlorine removal agent thereby form the mixture.
  • the chlorine-containing substance is thermally decomposed at a predetermined temperature thereby generating harmful chlorine-containing gas.
  • This chlorine-containing gas immediately reacts with the chlorine removal agent thus to form harmless chloride.
  • the chlorine removal process of this embodiment was carried out by using ,as the treatable material, polyvinylidene chloride which contained a large amount of chlorine components.
  • the chlorine removal agent sodium hydrogen carbonate
  • Example 1-1 No chlorine removal agent was added to 4g of the treatable material in Comparative Example 1-1.
  • a chlorine removal agent (slaked or hydrated lime) which was not within the scope of the present invention was add in an amount of 20 g to 4 g of the treatable material to form a mixture to be heated, in Comparative Example 1-2.
  • a chlorine removable agent (calcium carbonate) which was not within the scope of the present invention was added in an amount of 20 g to 4 g of the treatable material to form a mixture to be heated, in Comparative Example 1-3.
  • the chlorine removal agent was in the form of powder having an average particle size of 100 ⁇ m, in all Example and Comparative Examples.
  • the temperature at each of the eight steps was kept for 5 minutes, in which a concentration of hydrogen chloride gas in the tank was measured at each temperature rising time (at which the temperature was rising from one temperature step to the next temperature step) and at each temperature keeping time (at which the temperature at each temperature step was keeping).
  • the temperature rising time is indicated as “Rising time” while the temperature keeping time is indicated as “Keeping time” in Table 3.
  • the tank was provided with a gas discharge pipe through which gas and pressure generated in the tank upon heating was discharged out of the tank.
  • the measurement of the hydrogen chloride gas concentration was accomplished by using a detector tube according to JIS (Japanese Industrial Standard) - K0804, in which the detector tube was inserted into the gas discharge pipe to measure the hydrogen chloride gas concentration.
  • Results of the hydrogen chloride gas concentration measurement were shown in Table. 3. It is to be noted that ten times of the above experiment were repeated to obtain ten actual measured values of the hydrogen gas concentration for each Example and Comparative Example, in which the measured value (shown in Table 3) for each Example indicates the highest value in the measured values while the measured value (shown in Table 3) for each Comparative Example indicates the lowest value in the measured values. Additionally, “ND” in Table 3 indicates the fact that no hydrogen chloride gas was detected in any of 10 times hydrogen chloride gas concentration measurements to obtain the ten actual measured values. Further, manners of post-treatment for the chlorine removal agent were inspected and shown as "Post-treatment for chlorine removal agent" in Table 3.
  • the treatable material was prepared by mixing polyvinylidene chloride with a simulated trash in order that the treatable material was similar to standard urban trash and in order to carry out the experiment under a further severe condition.
  • 5g of sodium hydrogen carbonate was added as the chlorine removal agent to the treatable material which was prepared by mixing 1 g of polyvinylidene chloride to 20 g of the simulated trash thereby to form the mixture to be heated, in Example 1-2.
  • Sodium hydrogen carbonate in an amount of 2.5 g was added as the chlorine removal agent to the treatable material which was prepared by mixing 0.5 g of polyvinylidene chloride to 20 g of the simulated trash thereby forming the mixture to be heated, in Example 1-3.
  • Example 1-5 Sodium hydrogen carbonate in an amount of 0.5 g was added as the chlorine removal agent to the treatable material which was prepared by mixing 0.1 g of polyvinylidene chloride to 20 g of the simulated trash thereby forming the mixture to be heated, in Example 1-4.
  • Example 1-1 where sodium hydrogen carbonate was added as the chlorine removal agent to the treatable material, no generation of hydrogen chloride gas could be detected throughout the whole temperature regions in the heating process, demonstrating that the sodium hydrogen carbonate was very excellent for the chloride removal agent.
  • Example 1-3, 1-4 and 1-5 where various amounts of sodium hydrogen carbonate were added as the chlorine removal agent to the treatable material containing the simulated trash and polyvinylidene chloride, no generation of hydrogen chloride gas could be detected throughout the whole temperature regions in the heating process.
  • Example 1-5 where sodium hydrogen carbonate was added as the chlorine removal agent to the treatable material containing the simulated trash and water, generation of hydrogen chloride gas could hardly be detected throughout the whole temperature regions although a slight amount of hydrogen chloride gas was detected to be generated at the temperature rising and keeping times at 450 °C and at the temperature rising time at 500 °C.
  • the temperature for heating the mixture of the treatable material and the chlorine removal agent is preferably within a range of not higher than 1000 °C from the view point of the fact that a facility for carrying out the chlorine removal process of the present invention is required to be large-sized if the temperature is raised over 1000 °C.
  • the residue was left in the tank after the heating process had been completed.
  • the residue was subjected to inspection, upon which it was detected that the residue did not contain noxious chlorine-containing gas component and contained harmless chloride or sodium chloride.
  • the residue was put into water and stirred for 10 minutes, in which sodium chloride was dissolved in water while carbonized materials remained. It was also detected that the carbonized materials did not contain chlorine-containing gas component.
  • chlorine-containing compound and chlorine component in the treatable material can be converted into sodium chloride (NaCl), water (H 2 O) and carbon dioxide gas (CO 2 ), and therefore hydrogen chloride forming part of a source of dioxin cannot be formed thereby realizing the unexpected result of making both emitted gas and residue harmless.
  • the substance containing carbonate containing an alkali metal such as sodium carbonate, sodium hydrogen carbonate, sodium sesqui carbonate, natural soda (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O) is used as the chlorine removal agent.
  • Sodium carbonate can form monohydrate compound and decahydrate compound and is known as soda.
  • Sodium sesqui carbonate naturally exists as trona.
  • NaCl is formed.
  • NaCl is a harmless chloride and can be effectively removed under a rinsing or dissolving treatment with water or the like.
  • solid residual materials or carbonized materials remain in the tank and reusable. Accordingly, the residual materials can be separated into respective materials which are different in characteristics by any separating means. The separated respective materials are dried and massed to be usable as fuel or the like. Additionally, liquid (such as water) used for the above rinsing treatment hardly contains no noxious substances and therefore can be discharged as it is to a river and the sea.
  • the residue taken out from the tank contains harmless chloride or sodium chloride (NaCl).
  • NaCl sodium chloride
  • the residue is put into a water tank containing water, and stirred for a predetermined time thereby dissolving sodium chloride.
  • solid materials in the water tank are taken out from the water tank and then are subjected to a centrifugal dehydration to separate water content from the solid materials.
  • the thus dehydrated solid materials are dried and hardened into a mass. Water remaining in the water tank and the separated water content are drained through a separate draining and treatment means.
  • carbon contents in the hardened mass can be used as fuel while inorganic contents in the hardened mass can be used as materials for glass and cement.
  • the residue can be separated into respective materials which are different in characteristics by any separating means, upon which the separated respective materials are dried and massed to be effectively used as fuel or the like.
  • the noxious component or chlorine removal agent contains at least one alkali metal hydroxide, i.e., at least one of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), and cesium hydroxide (CsOH).
  • alkali metal hydroxide i.e., at least one of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), and cesium hydroxide (CsOH).
  • sodium hydroxide NaOH
  • HCl hydrogen chloride
  • alkali metal hydroxide is added to and mixed with the treatable material as the chlorine removal agent thereby form the mixture.
  • the chlorine-containing substance is thermally decomposed at a predetermined temperature thereby generating harmful chlorine-containing gas.
  • This chlorine-containing gas immediately reacts with the chlorine removal agent thus to form harmless chloride.
  • the chlorine removal process of this experiment was carried out by using ,as the treatable material, polyvinylidene chloride which contained a large amount of chlorine components.
  • the chlorine removal agent pulverized sodium hydroxide
  • the chlorine removal agent pulverized potassium hydroxide
  • No chlorine removal agent was added to 1g and to 4g of the treatable material ,respectively, in Comparative Examples 2-1 and 2-2.
  • a chlorine removal agent (slaked or hydrated lime) which was not within the scope of the present invention in an amount of 20 g was added to 4 g of the treatable material to form a mixture to be heated, in Comparative Example 2-3.
  • a chlorine removable agent (calcium carbonate) which was not within the scope of the present invention in an amount of 20 g was added to 4 g of the treatable material to form a mixture to be heated, in Comparative Example 2-4.
  • the chlorine removal agent was in the form of powder having an average particle size of 100 ⁇ m, in all Example and Comparative Examples.
  • the treatable material in the above-mentioned amount was put into a tank or furnace, and then 20 g of the chlorine removal agent was added to and mixed with the treatable material in the tank to form the above-mentioned mixture, except for Comparative Examples 2-1 and 2-2. Then, the tank was tightly sealed so that the inside the tank was isolated from the outside air or atmospheric air in order that the mixture was subjected to dry distillation upon heating.
  • the thus sealed tank was stepwise heated with a heating coil, in which heating was made at eight temperature steps of 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C and 600 to 1000 °C.
  • the temperature at each of the nine steps was kept for 5 minutes, in which a concentration of hydrogen chloride gas in the tank was measured at each temperature rising time (at which the temperature was rising from one temperature step to the next temperature step) and at each temperature keeping time (at which the temperature at each temperature step was keeping).
  • the temperature rising time is indicated as “Rising time” while the temperature keeping time is indicated as “Keeping time” in Table 4.
  • the tank was provided with a gas discharge pipe through which gas and pressure generated in the tank upon heating was discharged out of the tank.
  • the measurement of the hydrogen chloride gas concentration was accomplished by using a detector tube according to JIS (Japanese Industrial Standard) - K0804, in which the detector tube was inserted into the gas discharge pipe to measure the hydrogen chloride gas concentration.
  • Results of the hydrogen chloride gas concentration measurement were shown in Fig. 4. It is to be noted that ten times of the above experiment were repeated to obtain ten actual measured values of the hydrogen gas concentration for each Example and Comparative Example, in which the measured value (shown in Table 4) for each Example indicates the highest value in the measured values while the measured value (shown in Table 4) for each Comparative Example indicates the lowest value in the measured values. Additionally, “ND” in Table 4 indicates the fact that no hydrogen chloride gas was detected in any of 10 times hydrogen chloride gas concentration measurements to obtain the ten actual measured values. Further, manners of post-treatment for the chlorine removal agent were inspected and shown as "Post-treatment for chlorine removal agent" in Table 4.
  • the alkali metal hydroxide serving as the chlorine removal agent can effectively convert noxious chlorine-containing gas into harmless chloride under a reaction in which the alkali metal reacts with chlorine to form chloride of alkali metal.
  • Preliminary tests (Comparative Examples 2-1 and 2-2) were conducted in which polyvinylidene chloride containing a large amount of chlorine component was used as the treatable material. As a result of these tests, it was confirmed that a large amount of hydrogen chloride was generated as shown in the column of Comparative Examples 2-1 and 2-2 in Table 4.
  • the temperature for heating the mixture of the treatable material and the chlorine removal agent is preferably within a range of not higher than 1000 °C from the view point of the fact that a facility for carrying out the chlorine removal process of the present invention is required to be large-sized if the temperature is raised over 1000 °C.
  • the residue was left in the tank after the heating process had been completed.
  • the residue was subjected to inspection, upon which it was detected that the residue did not contain noxious chlorine-containing gas component and contained harmless chloride (sodium chloride or potassium chloride).
  • the residue was put into water and stirred for 10 minutes, in which sodium or potassium chloride was dissolved in water while carbonized materials remained. It was also detected that the carbonized materials did not contain chlorine-containing gas component.
  • chlorine-containing compound and chlorine component in the treatable material can be converted into sodium or potassium chloride and water, and therefore hydrogen chloride forming part of a source of dioxin cannot be formed thereby realizing the unexpected results of making both emitted gas and residue harmless. It will be appreciated that the same results can be obtained even if at least one of other alkali metal hydroxides such as lithium hydroxide (LiOH), rubidium hydroxide (RbOH), and cesium hydroxide (CsOH) are used as the chlorine removal agent.
  • LiOH lithium hydroxide
  • RbOH rubidium hydroxide
  • CsOH cesium hydroxide
  • At least one alkali metal hydroxide i.e., sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), and/or cesium hydroxide (CsOH) is used as the chlorine removal agent.
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • LiOH lithium hydroxide
  • RbOH rubidium hydroxide
  • CsOH cesium hydroxide
  • NaCl and KCl are formed.
  • NaCl and KCl are harmless chlorides and can be effectively removed under a rinsing or dissolving treatment with water or the like.
  • solid residual materials or carbonized materials remain in the tank and reusable. Accordingly, the residual materials can be separated into respective materials which are different in characteristics by any separating means. The separated respective materials are dried and massed to be usable as fuel or the like. Additionally, liquid (such as water) used for the above rinsing treatment hardly contains no noxious substances and therefore can be discharged as it is to a river and the sea.
  • the residue taken out from the tank contains harmless sodium chloride (NaCl) and potassium chloride (KCl).
  • NaCl sodium chloride
  • KCl potassium chloride
  • the residue is put into a water tank containing water, and stirred for a predetermined time thereby dissolving sodium and potassium chlorides.
  • solid materials in the water tank are taken out from the water tank and then are subjected to a centrifugal dehydration to separate water content from the solid materials.
  • the thus dehydrated solid materials are dried and massed. Water remaining in the water tank and the separated water content are drained through a separate draining and treatment means.
  • carbon contents in the massed solid materials can be used as fuel while inorganic contents in the massed solid materials can be used as materials for glass and cement.
  • the residue can be separated into respective materials which are different in characteristics by any separating means, upon which the separated respective materials are dried and massed to be effectively used as fuel or the like.
  • the noxious component chlorine removal agent contains alkali metal hydrogen carbonate and/or alkali metal carbonate, i.e., at least one of sodium hydrogen carbonate, sodium carbonate, sodium sesqui carbonate, and natural soda.
  • alkali metal hydrogen carbonate and/or alkali metal carbonate i.e., at least one of sodium hydrogen carbonate, sodium carbonate, sodium sesqui carbonate, and natural soda.
  • polyvinyl chloride and polyvinylidene chloride are used as the treatable material in this embodiment.
  • sodium hydrogen carbonate (NaHCO 3 ) is used as the chlorine removal agent, in which the sodium hydrogen carbonate is mixed with the treatable material and heated thereby bringing about the following reaction with hydrogen chloride (HCl) which is a major chlorine-containing compound contained in gases generated from the treatable material upon heating: NaHCO 3 + HCl ⁇ NaCl + H 2 O + CO 2 .
  • HCl hydrogen chloride
  • alkali metal carbonate and/or alkali metal hydrogen carbonate are added to and mixed with the treatable material as the chlorine removal agent thereby form the mixture.
  • the chlorine-containing substance is thermally decomposed at a predetermined temperature thereby generating harmful chlorine-containing gas.
  • This chlorine-containing gas immediately reacts with the chlorine removal agent thus to form harmless chloride.
  • the chlorine removal process of this experiment was carried out by using ,as the treatable material, polyvinyl chloride and polyvinylidene chloride which contained a large amount of chloride components.
  • 20 g of the chlorine removal agent (sodium hydrogen carbonate) was added to 4 g of the treatable material (polyvinyl chloride) to form a mixture to be heated, in Example 3-1.
  • the chlorine removal agent (sodium hydrogen carbonate) in an amount of 20g was added to 4 g of the treatable material (polyvinylidene chloride) to form a mixture to be heated, in Example 3-2.
  • No chlorine removal agent was added to 4g of the treatable material (polyvinylidene chloride) in Comparative Example 3-1.
  • a chlorine removal agent (calcium carbonate) which was not within the scope of the present invention was add in an amount of 20 g to 4 g of the treatable material (polyvinylidene chloride) to form a mixture to be heated, in Comparative Example 3-2.
  • a chlorine removable agent (slaked lime) which was not within the scope of the present invention was added in an amount of 20 g to 4 g of the treatable material (polyvinylidene chloride) to form a mixture to be heated, in Comparative Example 3-3.
  • the chlorine removal agent was in the form of powder having an average particle size of 100 ⁇ m, in all Example and Comparative Examples.
  • Example 3-1 In the experiment for each Example or Comparative Example, 4 g of the treatable material was put into a tank or furnace, and then 20 g of the chlorine removal agent was added to and mixed with the treatable material in the tank to form the above-mentioned mixture, except for Comparative Example 3-1. Then, the tank was tightly sealed so that the inside the tank was isolated from the outside air or atmospheric air in order that the mixture was subjected to dry distillation upon heating. The thus sealed tank was stepwise heated with a heating coil, in which heating was made at eight temperature steps of 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C.
  • the temperature at each of the eight steps was kept for 5 minutes, in which a concentration of hydrogen chloride gas in the tank was measured at each temperature rising time (at which the temperature was rising from one temperature step to the next temperature step) and at each temperature keeping time (at which the temperature at each temperature step was keeping).
  • the temperature rising time is indicated as “Rising time” while the temperature keeping time is indicated as “Keeping time” in Table 5.
  • the tank was provided with a gas discharge pipe through which gas and pressure generated in the tank upon heating was discharged out of the tank.
  • the measurement of the hydrogen chloride gas concentration was accomplished by using a detector tube according to JIS (Japanese Industrial Standard) - K0804, in which the detector tube was inserted into the gas discharge pipe to measure the hydrogen chloride gas concentration.
  • Results of the hydrogen chloride gas concentration measurement were shown in Table 5. It is to be noted that ten times of the above experiment were repeated to obtain ten actual measured values of the hydrogen gas concentration for each Example and Comparative Example, in which the measured value (shown in Table 5) for each Example indicates the highest value in the measured values while the measured value (shown in Table 5) for each Comparative Example indicates the lowest value in the measured values. Additionally, “ND” in Table 5 indicates the fact that no hydrogen chloride gas was detected in any of 10 times hydrogen chloride gas concentration measurements to obtain the ten actual measured values. Further, manners of post-treatment for the chlorine removal agent were inspected and shown as "Post-treatment for chlorine removal agent" in Table 5.
  • Example 3-2 where sodium hydrogen carbonate was added as the chlorine removal agent to the treatable material, no generation of hydrogen chloride gas could be detected throughout the whole temperature regions in the heating process, demonstrating that the sodium hydrogen carbonate was very excellent as the chloride removal agent.
  • Example 3-1 where sodium hydrogen carbonate was added as the chlorine removal agent to the other treatable material (polyvinyl chloride), generation of hydrogen chloride gas could be completely suppressed throughout the whole temperature regions in the heating process.
  • the temperature for heating the mixture of the treatable material and the chlorine removal agent is preferably within a range of not higher than 1000 °C from the view point of the fact that a facility for carrying out the chlorine removal process of the present invention is required to be large-sized if the temperature is raised over 1000 °C.
  • the residue was left in the tank after the heating process had been completed.
  • the residue was subjected to inspection, upon which it was detected that the residue did not contain noxious chlorine-containing gas component and contained harmless chloride or sodium chloride.
  • the residue was put into water and stirred for 10 minutes, in which sodium chloride was dissolved in water while carbonized materials remained. It was also detected that the carbonized materials did not contain chlorine-containing gas component.
  • chlorine-containing compound and chlorine component in the treatable material can be converted into sodium chloride (NaCl), water (H 2 O) and carbon dioxide gas (CO 2 ), and therefore hydrogen chloride forming part of a source of dioxin cannot be formed thereby realizing the unexpected result of making both emitted gas and residue harmless.
  • sodium carbonate, sodium hydrogen carbonate, and/or sodium sesqui carbonate natural soda is used as the chlorine removal agent.
  • Sodium carbonate can form monohydrate compound and decahydrate compound and is known as soda.
  • Sodium sesqui carbonate naturally exists as trona.
  • NaCl is formed.
  • NaCl is a harmless chloride and can be effectively removed under a rinsing or dissolving treatment with water or the like.
  • solid residual materials or carbonized materials remain in the tank and reusable. Accordingly, the residual materials can be separated into respective materials which are different in characteristics by any separating means. The separated respective materials are dried and massed to be usable as fuel or the like.
  • liquid (such as water) used for the above rinsing treatment hardly contains no noxious substances and therefore can be discharged as it is to a river and the sea.
  • the noxious component or chlorine removal agent contains alkali metal hydrogen carbonate and/or alkali metal carbonate, i.e., at least one of potassium hydrogen carbonate (KHCO 3 ) and potassium carbonate (K 2 CO 3 ), and used in the chlorine removal process for the treatable material which is polyvinyl chloride, polyvinylidene chloride, a synthetic resin containing chlorine, a rubber containing chlorine, and/or the like.
  • alkali metal hydrogen carbonate and/or alkali metal carbonate i.e., at least one of potassium hydrogen carbonate (KHCO 3 ) and potassium carbonate (K 2 CO 3 )
  • KHCO 3 potassium hydrogen carbonate
  • K 2 CO 3 potassium carbonate
  • sodium hydrogen carbonate (KHCO 3 ) is used as the chlorine removal agent, in which the sodium hydrogen carbonate is mixed with the treatable material and heated thereby bringing about the following reaction with hydrogen chloride (HCl) which is a major chlorine-containing compound contained in gases generated from the treatable material upon heating.
  • HCl hydrogen chloride
  • alkali metal carbonate and/or alkali metal hydrogen carbonate are added to and mixed with the treatable material as the chlorine removal agent thereby to form the mixture.
  • the chlorine-containing substance is thermally decomposed at a predetermined temperature thereby generating harmful chlorine-containing gas.
  • This chlorine-containing gas immediately reacts with the chlorine removal agent thus to form harmless chloride.
  • the chlorine removal process of this embodiment was carried out by using, as the treatable material, polyvinylidene chloride or the simulated (standard) trash which contained a large amount of chlorine components.
  • the simulated trash was the same as that used in the experiments for the first embodiment.
  • 10 g of the chlorine removal agent (pulverized potassium hydrogen carbonate) was added to 4 g of the treatable material (polyvinylidene chloride) to form a mixture to be heated, in Example 4-1.
  • the chlorine removal agent (pulverized potassium hydrogen carbonate) in an amount of 10 g was added to 4 g of the treatable material (the simulated trash) to form a mixture to be heated, in Example 4-2.
  • No chlorine removal agent was added to 4g of the treatable material (polyvinylidene chloride) in Comparative Example 4-1.
  • a chlorine removal agent (slaked lime) which was not within the scope of the present invention was added in an amount of 20 g to 4 g of the treatable material to form a mixture to be heated, in Comparative Example 4-2.
  • a chlorine removable agent (calcium carbonate) which was not within the scope of the present invention was added in an amount of 20 g to 4 g of the treatable material (polyvinylidene chloride) to form a mixture to be heated, in Comparative Example 4-3.
  • the chlorine removal agent was in the form of powder having an average particle size of 100 ⁇ m, in all Examples and Comparative Examples.
  • the predetermined amount of the treatable material was put into a tank or furnace, and then 20 g of the chlorine removal agent was added to and mixed with the treatable material in the tank to form the above-mentioned mixture, except for Comparative Example 4-1. Then, the tank was tightly sealed so that the inside the tank was isolated from the outside air or atmospheric air in order that the mixture was subjected to dry distillation upon heating. The thus sealed tank was stepwise heated with a heating coil, in which heating was made at eight temperature steps of 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C.
  • the temperature at each of the eight steps was kept for 5 minutes, in which a concentration of hydrogen chloride gas in the tank was measured at each temperature rising time (at which the temperature was rising from one temperature step to the next temperature step) and at each temperature keeping time (at which the temperature at each temperature step was keeping).
  • the temperature rising time is indicated as “Rising time” while the temperature keeping time is indicated as “Keeping time” in Table 6.
  • the tank was provided with a gas discharge pipe through which gas and pressure generated in the tank upon heating was discharged out of the tank.
  • the measurement of the hydrogen chloride gas concentration was accomplished by using a detector tube according to JIS (Japanese Industrial Standard) - K0804, in which the detector tube was inserted into the gas discharge pipe to measure the hydrogen chloride gas concentration.
  • Results of the hydrogen chloride gas concentration measurement were shown in Table. 6. It is to be noted that ten times of the above experiment were repeated to obtain ten actual measured values of the hydrogen gas concentration for each Example and Comparative Example, in which the measured value (shown in Table 6) for each Example indicates the highest value in the measured values while the measured value (shown in Table 6) for each Comparative Example indicates the lowest value in the measured values. Additionally, “ND” in Table 6 indicates the fact that no hydrogen chloride gas was detected in any of 10 times hydrogen chloride gas concentration measurements to obtain the ten actual measured values. Further, manners of post-treatment for the chlorine removal agent were inspected and shown as "Post-treatment for chlorine removal agent" in Table 6.
  • Example 4-1 where potassium hydrogen carbonate was added as the chlorine removal agent to the treatable material, no generation of hydrogen chloride gas could be detected throughout the whole temperature regions in the heating process, demonstrating that the potassium hydrogen carbonate was very excellent for the chloride removal agent.
  • Examples 4-2 where potassium hydrogen carbonate was added as the chlorine removal agent to the treatable material (the simulated trash), generation of a slight amount of hydrogen chloride was found; however, no substantial generation of hydrogen chloride gas could be detected throughout the whole temperature regions in the heating process.
  • KHCO 3 potassium hydrogen carbonate
  • HCl hydrogen chloride
  • potassium hydrogen carbonate reacts with hydrogen chloride thereby to form harmless potassium chloride and carbon dioxide gas.
  • potassium carbonate reacts with hydrogen chloride thereby to form harmless potassium chloride, water and carbon dioxide gas.
  • KCl is formed.
  • KCl is a harmless chloride and can be effectively removed under a rinsing or dissolving treatment with water or the like.
  • solid residual materials or carbonized materials remain in the tank and reusable. Accordingly, the residual materials can be separated into respective materials which are different in characteristics by any separating means. The separated respective materials are dried and massed to be usable as fuel or the like. Additionally, liquid (such as water) used for the above rinsing treatment hardly contains no noxious substances and therefore can be discharged as it is to a river and the sea.
  • the residue taken out from the tank contains harmless chloride or potassium chloride (KCl).
  • KCl potassium chloride
  • the residue is put into a water tank containing water, and stirred for a predetermined time thereby dissolving sodium chloride.
  • solid materials in the water tank are taken out from the water tank and then are subjected to a centrifugal dehydration to separate water content from the solid materials.
  • the thus dehydrated solid materials are dried and massed. Water remaining in the water tank and the separated water content are drained through a separate draining and treatment means.
  • carbon contents in the massed solid materials can be used as fuel while inorganic contents in the hardened mass can be used as materials for glass and cement.
  • the residue can be separated into respective materials which are different in characteristics by any separating means, upon which the separated respective materials are dried and massed to be effectively used as fuel or the like.
  • This noxious component removal process is for removing noxious component (such as chlorine and/or sulfur) from a treatable material (such as urban waste or trash, or industrial waste) containing the noxious component (such as chlorine and/or sulfur).
  • the treatable material may contain polyvinyl chloride, polyvinylidene chloride, a synthetic resin containing chlorine, a rubber containing chlorine, so-called shredder dust (dust or trash produced by a paper-shredder), articles formed of polyvinyl chloride or polyvinylidene chloride, used tires, and formed polystyrene.
  • the noxious component removal process of this embodiment comprises the following steps in the sequence set forth: (a) mixing the treatable material and a noxious component (chloride and/or sulfur) removal agent to form a mixture, the noxious removal agent containing an alkali metal compound; and (b) heating the mixture to thermally decompose the treatable material to generate a noxious component (chlorine and/or sulfur)-containing substance and cause the noxious component-containing substance to contact and react with the noxious component removal agent to form a harmless compound.
  • the noxious component removal agent contains at least one of alkali metal carbonate, alkali metal hydrogen carbonate, and alkali metal hydroxide, i.e., at least one of sodium hydrogen carbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), and potassium hydrogen carbonate (KHCO 3 ), potassium sodium carbonate (KNaCO 3 ⁇ 6H 2 O).
  • sodium hydrogen carbonate NaHCO 3
  • sodium carbonate Na 2 CO 3
  • sodium sesqui carbonate Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O
  • natural soda containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O
  • sodium hydroxide NaOH
  • KOH potassium hydroxide
  • KOH
  • sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide is used to be mixed with the treatable material which contains a large amount of chlorine and sulfur.
  • the chloride removal agent is added to and mixed with the treatable material thereby to form the mixture.
  • the chlorine-containing substance is thermally decomposed at a predetermined temperature thereby generating harmful chlorine-containing gas and sulfur-containing gas.
  • This chlorine-containing gas and sulfur-containing gas immediately react with the noxious component removal agent thus to form harmless chloride (NaCl, KCl) and sulfite (Na 2 SO 3 , K 2 SO 3 ).
  • the chlorine and sulfur removal system comprises a mixing means or device 1 for mixing the treatable material (such as pulverized waste or trash) and the noxious component removal agent (such as sodium hydrogen carbonate) to form a mixture.
  • a thermal treatment furnace 2 is formed cylindrical and rotatable. The mixture formed by the mixing device 1 is supplied into the furnace 2. The mixture may be formed by other means or devices than the mixing device 1.
  • the thermal treatment furnace 2 is provided with a rotating transferring means or device (not shown) which is adapted to transfer the mixture under stirring. In the furnace 2, the mixture of the treatable material and the noxious component removal agent is heated in the low oxygen concentration atmosphere to accomplish thermal decomposition of the treatable material.
  • the furnace 2 is provided with a heating coil 2 for heating the content of the furnace 2.
  • a residue treatment means or device 4 is provided to treat the residue (ash) formed upon heating the treatable material in the furnace 2.
  • the residue is taken out of the furnace 2 and subjected to a solid-liquid separation.
  • the residue is rinsed with liquid such as water so that formed chloride and/or sulfite are separated and removed and then taken out from a liquid discharge section 4a.
  • the residual solid such as metals and carbonized materials are taken out from a solid take-out section 4b.
  • Emitted gas from the thermal treatment furnace 2 is introduced into an emitted gas treatment means or device 5. It will be understood that the emitted gas has been made harmless because the noxious components in the treatable material is removed under the action of the noxious component removal agent.
  • a necessary treatment is made to the introduced emitted gas in the emitted gas treatment device 5.
  • the treated gas from the gas treatment device 5 is then introduced into a gas recovery means or device 6 for recover the gas or into a secondary combustion means or device 7 to make secondary combustion of the gas to be discharged.
  • the treatable material containing the noxious component(s) and the noxious component removal agent (such as sodium hydrogen carbonate) are cast into the mixing device 1 and sufficiently mixed with each other, and then cast into the thermal treatment furnace 2.
  • the treatable material may be pulverized prior to being cast, or pulverized simultaneously with mixing between the treatable material and the noxious component removal agent.
  • the amount of the noxious component removal agent is within a range of from 5 to 30 % by weight relative to the treatable material.
  • the thermal treatment or heating of the mixture in the thermal treatment furnace 2 is accomplished within temperature and time ranges to cover the temperature and time of generation of HCl gas and SOx gas from the treatable material, the temperature (for example, 600 °C) and time (for example, 1 hour) having been determined under a previous investigation.
  • These temperature and time are in relation to a condition (such as the size and the heating coil) of the thermal treatment furnace, the treatment amount of the treatable material, the treatment time of the thermal treatment of the treatable material, the treatment temperature of the thermal treatment of the treatable material. Therefore, the above temperature and time are required to be previously determined under a sufficient investigation and to accumulate the data to be taken for the temperature and time.
  • the thermal treatment in this process is under a heating condition for accomplishing dry distillation (or thermal decomposition) of the treatable material and therefore is not under another heating condition for accomplishing combustion or incineration of the treatable material.
  • noxious HCl gas and SOx gas can be effectively react with each other upon contact of them, so that noxious HCl gas and SOx gas are converted respectively into harmless chloride and sulfite.
  • a total reaction atmosphere or circumference inside the thermal treatment furnace can meet necessary conditions and be stable.
  • the stable low oxygen concentration atmosphere is formed inside the thermal treatment furnace.
  • decomposition gas containing HCl gas and SOx gas are generated, in which HCl and SOx components immediately react with the noxious component removal agent or sodium hydrogen carbonate thereby to form harmless chloride (such as NaCl) and sulfite (Na 2 SO 3 ), so that noxious HCl and SOx are removed from the decomposition gas.
  • the residue formed upon the thermal treatment of the treatable material contains no noxious HCl and SOx.
  • the decomposition gas and the residue can be simultaneously made harmless.
  • the residue is taken out through the residue treatment device 4 and rinsed with water or a solution thereby to separate the chloride and the sulfite from the residue, leaving solid residual material.
  • the solid residual material contains useful metals which are effectively reusable.
  • RDF refused derived fuel
  • RDF used in the experiments contained 60.173 % by weight of carbon (C), 16.277 % by weight of oxygen (O), 10.745 % by weight of silicon (Si), 7.045 % by weight of calcium (Ca), 3.314 % by weight of aluminum (Al), 0.888 % by weight of magnesium (Mg), 0.505 % by weight of phosphorus (P), 0.466 % by weight of chlorine (Cl), 0.331 % by weight of sulfur (S), and 0.155 % by weight of potassium (K), 0.101 % by weight of sodium (Na).
  • Example 5-1 10 g of the chlorine removal agent (sodium hydrogen carbonate) was added to 40 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-1.
  • the chlorine removal agent (sodium hydrogen carbonate) in an amount of 4g was added to 40 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-2.
  • the chlorine removal agent (potassium hydrogen carbonate) in an amount of 3 g was added to 40 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-3.
  • the chlorine removal agent (sodium carbonate and potassium carbonate) in an amount of 3 g was added to 20 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-4.
  • the chlorine removal agent (sodium hydroxide) in an amount of 3 g was added to 20 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-5.
  • the chlorine removal agent (potassium hydroxide) in an amount of 3 g was added to 20 g of the treatable material (crushed RDF) to form a mixture to be heated, in Example 5-6.
  • the chlorine removal agent sodium hydrogen carbonate
  • the chlorine removal agent was in the form of powder having an average particle size of 100 ⁇ m, in all Examples
  • the experiment for each Example was conducted as follows: A predetermined amount of the treatable material was put into a tank or furnace, and then 20 g of the noxious component removal agent was added to and mixed with the treatable material in the tank to form the above-mentioned mixture.
  • a predetermined amount of the treatable material was put into a tank or furnace. Then, the tank was tightly sealed so that the inside the tank was isolated from the outside air or atmospheric air in order that the mixture or only the treatable material was subjected to dry distillation upon heating.
  • the thus sealed tank was stepwise heated with a heating coil, in which heating was made at eight temperature steps of 250 °C, 300 °C, 350 °C, 400 °C, 450 °C, 500°C, 550°C, 600 °C.
  • the temperature at each of the eight steps was kept for 5 minutes, in which a concentration of HCl gas and a concentration of SO 2 in the tank was measured at each temperature rising time (at which the temperature was rising from one temperature step to the next temperature step) and at each temperature keeping time (at which the temperature at each temperature step was keeping).
  • the temperature rising time is indicated as "Rising time” while the temperature keeping time is indicated as "Keeping time” in Tables 7 and 8.
  • the tank was provided with a gas discharge pipe through which gas and pressure generated in the tank upon heating was discharged out of the tank.
  • the measurement of the hydrogen chloride gas concentration was accomplished by using a detector tube according to JIS (Japanese Industrial Standard) - K0804, in which the detector tube was inserted into the gas discharge pipe to measure HCl and SO 2 gas concentrations. Results of HCl and SO 2 gas concentration measurement were shown in Tables 7 and 8. It is to be noted that ten times of the above experiment were repeated to obtain ten actual measured values of the hydrogen gas concentration for each Example and Comparative Example, in which the measured value (shown in Table 7) for each Example indicates the highest value in the measured values while the measured value (shown in Table 8) for each Comparative Example indicates the lowest value in the measured values.
  • ND in Tables 7 and 8 indicates the fact that no hydrogen chloride gas was detected in any of 10 times HCl and SO 2 gas concentration measurements to obtain the ten actual measured values. Further, manners of post-treatment for the noxious component removal agent were inspected and shown as "Post-treatment for chlorine removal agent" in Tables 7 and 8.
  • the temperature for heating the mixture of the treatable material and the chlorine removal agent may be selected according to form of facilities for accomplish the thermal treatment, time of the thermal treatment, amount of the treatable material and the like.
  • sodium hydrogen carbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), and potassium hydrogen carbonate (KHCO 3 ) can react with noxious HCl thereby to convert HCl into harmless chloride (NaCl and KCl) according to reaction formulae discussed before. It will be understood that sodium potassium carbonate and sodium carbonate hydrate can also react with noxious HCl similarly to the above.
  • NaOH or KOH smoothly reacts with HCl thereby to newly form harmless chloride (NaCl , KCl).
  • the residue was left in the tank after the heating process had been completed.
  • the residue was subjected to inspection, upon which it was detected that the residue did not contain noxious chlorine-containing gas component and contained harmless chloride (sodium chloride or potassium chloride).
  • the residue was put into water and stirred for 10 minutes, in which the chloride was dissolved in water while carbonized materials remained. It was also detected that the carbonized materials did not contain chlorine-containing gas component.
  • chlorine-containing compound and chlorine component in the treatable material can be converted into sodium chloride (NaCl), potassium chloride (KCl), water (H 2 O) and carbon dioxide gas (CO 2 ), and therefore hydrogen chloride forming part of a source of dioxin cannot be formed thereby realizing the unexpected result of making both emitted gas and residue harmless.
  • CO 2 is separated at a temperature below a level (not lower than 300 °C) at which sulfur oxide (SO 2 ) is generated upon decomposition of the treatable material, forming NaOH or KOH. It is supposed that this forms an atmosphere in which reaction between NaOH or KOH and SO 2 is made smoothly.
  • SO 2 sulfur oxide
  • NaOH or KOH smoothly reacts with SO2 thereby to newly form harmless sulfite (Na 2 SO 3 , K 2 SO 3 ).
  • sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), potassium carbonate (K 2 CO 3 ), and sodium carbonate hydrate can react with noxious SO 2 thereby to convert SO 2 into harmless chloride sulfite (Na 2 SO 3 , K 2 SO 3 ) according to reaction formulae discussed hereinbefore.
  • sulfur-containing compound and sulfur component in the treatable material can be converted into sodium sulfite (Na 2 SO 3 ) in powder form, and potassium sulfite (K 2 SO 3 ) in powder form, water (H 2 O) and carbon dioxide gas (CO 2 ), and therefore SOx gas can be prevented from generation thus realizing the unexpected result of making both emitted gas and residue harmless.
  • the noxious component removal agent contains at least one of alkali metal carbonate, alkali metal hydrogen carbonate, and alkali metal hydroxide, i.e., at least one of sodium hydrogen carbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium sesqui carbonate (Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), natural soda (containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), and potassium hydrogen carbonate (KHCO 3 ), potassium sodium carbonate (KNaCO 3 ⁇ 6H 2 O).
  • sodium hydrogen carbonate NaHCO 3
  • sodium carbonate Na 2 CO 3
  • sodium sesqui carbonate Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O
  • natural soda containing Na 2 CO 3 ⁇ NaHCO 3 ⁇ 2H 2 O
  • sodium hydroxide NaOH
  • KOH potassium hydroxide
  • KOH
  • noxious hydrogen chloride and/or sulfur oxide are converted into harmless chloride (NaCl, KCl) and/or sulfite (Na 2 SO 3 , K 2 SO 3 ), thereby making it possible to remove noxious components (hydrogen chloride and/or sulfur oxide) from the decomposition gas generated from the treatable material upon heating.
  • the decomposition gas or emitted gas from the furnace can be effectively made harmless.
  • the chloride and/or sulfite form part of the residue and can be effectively removed under a rinsing or dissolving treatment with water or the like.
  • the residual materials can be separated into respective materials which are different in characteristics by any separating means.
  • the separated respective materials are dried and massed to be usable as fuel or the like.
  • liquid (such as water) used for the above rinsing treatment hardly contains no noxious substances and therefore can be discharged as it is to a river and the sea.

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Treating Waste Gases (AREA)
  • Processing Of Solid Wastes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Hardware Redundancy (AREA)
  • Removal Of Specific Substances (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
EP98102829A 1997-02-24 1998-02-18 Verfahren und System zur Entfernung von Schadstoffen Expired - Lifetime EP0860183B1 (de)

Applications Claiming Priority (21)

Application Number Priority Date Filing Date Title
JP9038729A JPH10235149A (ja) 1997-02-24 1997-02-24 塩化ビニル系物質の脱塩素処理方法
JP38737/97 1997-02-24
JP9038728A JPH10235148A (ja) 1997-02-24 1997-02-24 脱塩素処理方法
JP38726/97 1997-02-24
JP3873797 1997-02-24
JP9038737A JPH10235311A (ja) 1997-02-24 1997-02-24 塩化ビニル系物質の脱塩素処理方法
JP3872997 1997-02-24
JP38729/97 1997-02-24
JP3872897 1997-02-24
JP38728/97 1997-02-24
JP9038726A JPH10235147A (ja) 1997-02-24 1997-02-24 脱塩素処理方法
JP3872697 1997-02-24
JP9160911A JPH119938A (ja) 1997-06-18 1997-06-18 脱塩素処理方法
JP160911/97 1997-06-18
JP16091497 1997-06-18
JP9160914A JPH119939A (ja) 1997-06-18 1997-06-18 塩化ビニル系物質の脱塩素処理方法
JP160914/97 1997-06-18
JP16091197 1997-06-18
JP26599397 1997-09-30
JP9265993A JPH11101417A (ja) 1997-09-30 1997-09-30 有害ガスの発生防止方法
JP265993/97 1997-09-30

Publications (3)

Publication Number Publication Date
EP0860183A2 true EP0860183A2 (de) 1998-08-26
EP0860183A3 EP0860183A3 (de) 1999-01-20
EP0860183B1 EP0860183B1 (de) 2002-11-13

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KR (1) KR100341551B1 (de)
CN (1) CN1095687C (de)
AT (1) ATE227598T1 (de)
AU (1) AU714634B2 (de)
DE (1) DE69809310T2 (de)
DK (1) DK0860183T3 (de)
ES (1) ES2186931T3 (de)
MY (1) MY121329A (de)
NO (1) NO316905B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101597387B (zh) * 2009-05-22 2011-12-07 上海岚淼水处理科技有限公司 用于工业水处理的多糖纳米除氯剂的制备方法
CN105307755A (zh) * 2013-06-13 2016-02-03 科莱恩公司 用于减少气体流中的卤化物浓度的方法和活性材料

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104971609B (zh) * 2015-07-22 2017-04-05 南京格洛特环境工程股份有限公司 一种氟化氢废气治理及资源化利用的方法及设备
CN108339365B (zh) * 2017-01-24 2020-09-25 内蒙古大学 一种用于控制化工工业废气排放的装置及方法
CN109001007A (zh) * 2018-08-22 2018-12-14 汉能新材料科技有限公司 一种物料的处理方法

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EP0372276A1 (de) * 1988-11-25 1990-06-13 Rwe- Entsorgung Aktiengesellschaft Verfahren zur Aufarbeitung kontaminierter Öle
US4938936A (en) * 1988-09-01 1990-07-03 Mobil Oil Corporation Hydrogen fluoride vapor containment and neutralization
WO1996029118A1 (en) * 1995-03-22 1996-09-26 Nkt Research Center A/S A method for treatment of halogen-containing waste material

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US5064526A (en) * 1990-04-27 1991-11-12 The United States Of America As Represented By The Administrator Of The Environmental Protection Agency Method for the base-catalyzed decomposition of halogenated and non-halogenated organic compounds in a contaminated medium
US5039350A (en) * 1990-04-27 1991-08-13 The United States Of America As Represented By The Administrator Of The Environmental Protection Agency Method for the decomposition of halogenated organic compounds in a contaminated medium
JP3288164B2 (ja) * 1993-12-28 2002-06-04 株式会社東芝 廃プラスチックの熱分解装置
JP3213134B2 (ja) * 1993-09-13 2001-10-02 株式会社東芝 加熱油化方法及びその装置
JPH06179877A (ja) * 1991-12-20 1994-06-28 Toshiba Corp 廃プラスチックの熱分解方法及び装置
CA2159521C (en) * 1994-10-07 1999-11-09 Shigeo Iiyama Method for desulfurizing exhaust gas

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Publication number Priority date Publication date Assignee Title
US4938936A (en) * 1988-09-01 1990-07-03 Mobil Oil Corporation Hydrogen fluoride vapor containment and neutralization
EP0372276A1 (de) * 1988-11-25 1990-06-13 Rwe- Entsorgung Aktiengesellschaft Verfahren zur Aufarbeitung kontaminierter Öle
WO1996029118A1 (en) * 1995-03-22 1996-09-26 Nkt Research Center A/S A method for treatment of halogen-containing waste material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101597387B (zh) * 2009-05-22 2011-12-07 上海岚淼水处理科技有限公司 用于工业水处理的多糖纳米除氯剂的制备方法
CN105307755A (zh) * 2013-06-13 2016-02-03 科莱恩公司 用于减少气体流中的卤化物浓度的方法和活性材料

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DK0860183T3 (da) 2003-03-10
AU5632998A (en) 1998-08-27
EP0860183A3 (de) 1999-01-20
DE69809310D1 (de) 2002-12-19
NO980758L (no) 1998-08-25
NO980758D0 (no) 1998-02-23
DE69809310T2 (de) 2003-03-20
CN1095687C (zh) 2002-12-11
MY121329A (en) 2006-01-28
KR19980071609A (ko) 1998-10-26
KR100341551B1 (ko) 2002-08-22
CN1197685A (zh) 1998-11-04
AU714634B2 (en) 2000-01-06
ES2186931T3 (es) 2003-05-16
EP0860183B1 (de) 2002-11-13
NO316905B1 (no) 2004-06-21
ATE227598T1 (de) 2002-11-15

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