WO2007086667A1 - Method for processing waste insulating oil which contains polychlorinated biphenyls using electron-beam - Google Patents
Method for processing waste insulating oil which contains polychlorinated biphenyls using electron-beam Download PDFInfo
- Publication number
- WO2007086667A1 WO2007086667A1 PCT/KR2007/000380 KR2007000380W WO2007086667A1 WO 2007086667 A1 WO2007086667 A1 WO 2007086667A1 KR 2007000380 W KR2007000380 W KR 2007000380W WO 2007086667 A1 WO2007086667 A1 WO 2007086667A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- insulating oil
- waste insulating
- polychlorinated biphenyls
- electron beam
- pcbs
- Prior art date
Links
- 150000003071 polychlorinated biphenyls Chemical class 0.000 title claims abstract description 72
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000012545 processing Methods 0.000 title claims abstract description 18
- 230000001678 irradiating effect Effects 0.000 claims abstract description 15
- 231100000987 absorbed dose Toxicity 0.000 claims description 10
- 239000000126 substance Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SPJOZZSIXXJYBT-UHFFFAOYSA-N Fenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=CC=C1 SPJOZZSIXXJYBT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- -1 biphenyl polycyclic aromatic compound Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/0033—Heating devices using lamps
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
- H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/42—Heating elements having the shape of rods or tubes non-flexible
- H05B3/44—Heating elements having the shape of rods or tubes non-flexible heating conductor arranged within rods or tubes of insulating material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/032—Heaters specially adapted for heating by radiation heating
Definitions
- the present invention relates to a method for processing waste insulating oil which contains polychlorinated biphenyls by irradiating electron beam to the waste insulating oil.
- a transformer used for a certain period cannot be used any more because of changed physical properties of insulating oil as a component of the transformer and decrease of durability of other constituents, so that the insulating oil and other constituents of the transformer are discarded.
- insulating oil containing PCBS POLYCHLORINATED BIPHENYLS
- POPs Persistent Organic Pollutants
- dioxin one of residual organic pollutant having high toxicity.
- Polychlorinated biphenyls in general, are compounds wherein hydrogen atoms bonded at ten hydrogen atom position of a biphenyl (C 6 H 5 -C 6 H 5 ) are substituted by 1 ⁇ 10 chlorine atoms, having 242 kinds of isomers, theoretically. Among them, practically used are about 100 kinds.
- the polychlorinated biphenyls are not decomposed by heat up to 300 deg C, insoluble in water and show excellent electric insulation, so that it has been widely used in electric products such as transformers and condensers. Polychlorinated biphenyls, when being flowed into a sewage discharge plant as it is after use, cause environmental disruption and change of ecosystem.
- Polychlorinated biphenyls had been used without any particular environmental measure, but later on, it was found as a serious pollutant, so that the production and use have been prohibited all over the world since 1976.
- 1 million ton of polychlorinated biphenyls has been already discharged into nature throughout the world, and the amount to be discarded reaches about 2 million ton.
- Korea also, it is known that there is a large amount of polychlorinated biphenyls to be treated.
- a method for effectively decomposing polychlorinated biphenyls is urgently required.
- Biological processing using an enzyme, which is effective on treating polychlorinated biphenyls is advantageous in that it is applicable to various medium polluted by polychlorinated biphenyls, with generating minimum amount of residue.
- it is disadvantageous in that a long processing period is required, and the processing efficiency is largely affected by concentration of polychlorinated biphenyls.
- Thermal processing technique represented by burning-up is advantageous in that the processing speed is high, and the volume of the waste treated is small.
- it is disadvantageous in that it is restrictive to be used for liquid or gaseous medium, relative high cost is required, and additional treatment of the residue generated is needed.
- polychlorinated biphenyl containing product is burned in a common manner, it is reported that by-products such as polycyclic aromatic hydrocarbon including dioxin having higher toxicity than that of polychlorinated biphenyls, are produced.
- safe treatment of insulating oil containing polychlorinated biphenyls by means of burning is limited.
- Thermo-chemical processing techniques likewise thermal processing techniques, are disadvantageous in that additional treatment of the residue produced is required after the processing, while being advantageous in rapid processing speed and applicability to various medium polluted by polychlorinated biphenyls, as well as ability of treating high concentration of polychlorinated biphenyls to be utilized as a recycling technique.
- 1998-316798 describes a process for dechlorination by adding ethyl alcohol, ethylene glycol and alkaline hydroxide to an insulating oil containing polychlorinated biphenyls and irradiating ultraviolet ray in order to treat polychlorinated biphenyls contained in the insulating oil.
- Japanese Patent Laid-Open No. 2001-29942 describes a method to treat polychlorinated biphenyls contained in the insulating oil by using titanium oxide as a photo-catalyst.
- Decomposition process using ultraviolet ray has disadvantage of low decomposition efficiency.
- Chemical decomposition by use of an oxidant though the decomposition can be completed in several hours, has problem of corrosion of the material of the device.
- Oxidative decomposition by using ultra-critical water is troublesome because of excessive energy consumption.
- the object of the invention is to provide a process for treating waste insulating oil containing PCBs by irradiating electron beam to remove polychlorinated biphenyls (PCBs) contained in the waste insulating oil, maintaining the original properties of the treated oil.
- PCBs polychlorinated biphenyls
- the present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil. More specifically, it is characterized in that electron beam in a certain range is irradiated to selectively remove only PCBs contained in the waste insulating oil. Transformers used for a certain period are discarded because of reduced electric performance. Waste transformers consisting of various expensive metals can be decomposed and reused as resources, while PCBs used in transformers to enhance insulating property are environmentally harmful with high toxicity to require much care in reuse and handling.
- the present invention is characterized in that PCBs used in waste insulating oil containing PCBs in order to enhance insulating property of transformers are selectively removed, and electron beam is irradiated to the waste insulating oil containing PCBs to recover the physical properties of waste insulating oil to provide similar physical properties to initial insulating oil.
- PCBs are compounds wherein hydrogens at ten hydrogen atom position of a biphenyl (C6H5-C6H5) are substituted by 1-10 chlorine atom(s), represented by following chemical formula.
- the chemical bonds between the biphenyl polycyclic aromatic compound and chloride ion are easily detached with low ionization energy because of very low chemical bonding energy between them.
- the electron beam used according to the present invention is characterized in that it produces various kinds of chemical radicals (OH, 'H, e ⁇ , or the like) depending upon the ionization property , substances, and selectively decomposes chemical bonds in substances consisting of the chemical bonds.
- chemical radicals OH, 'H, e ⁇ , or the like
- PCBs according to the present invention is to irradiating said electron beam in a range from 1 kGy to 10,000 kGy on the basis of absorbed dose to the waste insulating oil containing PCBs.
- only PCBs contained in the waste insulating oil are selectively removed when the electron beam is irradiated in a range from 40 kGy to 70 kGy on the basis of absorbed dose.
- the electron beam is irradiated in a range from 20 kGy to
- the present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil containing PCBs. According to the invention, only PCBs contained in waste insulating oil can be selectively removed by irradiating electron beam to the waste insulating oil, thereby effectively treating the waste insulating oil containing PCBs.
- Fig. 1 is a graph showing the change of concentration of polychlorinated biphenyls versus absorbed energy dose of electron beam.
- Fig. 2 is a graph showing the change of viscosity of waste insulating oil versus absorbed energy dose of electron beam.
- Example 1 Change of concentration of PCBs and viscosity depending on the absorbed energy dose of electron beam
- Fig. 1 is a graph showing the change of concentration of PCBs contained in waste insulating oil, depending on the change of absorbed energy dose of electron beam.
- the initial concentration of PCBs in the waste insulating oil was 112 mg/L (ppm) , which was higher by 100,000 folds than 0.001 ppm, the detection limit of PCBs' concentration.
- the concentration of PCBs, 112 ppm was abruptly reduced by irradiation of 30 JcGy of electron beam on the basis of absorbed dose. It was found that the whole quantity of PCBs was removed at the dose of 50 kGy or more.
- Such results were obtained because the chemical bonds between the biphenyl and chloride ion are selectively decomposed and detached by electron beam due to weak bonding energy between the polyaromatic biphenyl and chloride ion in PCBs.
- Fig. 2 is a graph showing change of viscosity of waste insulating oil depending on the change of absorbed energy dose of electron beam.
- the viscosity of waste insulating oil containing PCBs was 8.911 cST at 40 ° C, which was higher than the viscosity (8.180 cST) of insulating oil before use.
- the change of viscosity is found to be caused by change of physical properties of insulation oil resulted from use of the transformer for a long period.
- the viscosity of the waste insulating oil having 8.911 cST of viscosity was reduced to the viscosity of the insulating oil before use, by irradiation of 30 kGy of electron beam on the basis of absorbed dose. With increasing the irradiation dose of electron beam, the viscosity of the waste insulating oil was slowly decreased.
- the viscosity can be tailored as required by irradiating electron beam in an appropriate range on the basis of absorbed dose.
- Table 1 shows change of physical properties when the waste insulating oil containing PCBs that had been treated by irradiating electron beam according to the present invention was reused in a transformer. It is found that pour point, refractive index, viscosity gravity constant and refractive index intercept of the waste insulating oil were same as those of the insulating oil before use, with only the specific gravity and viscosity being changed.
- Waste insulating oil before irradiating electron beam had specific gravity of 0.861, that was significantly higher than that of insulating oil before use, but the waste insulating oil containing PCBs, after treating by irradiation of electron beam, had specific gravity of 0.839 that is similar to that of insulating oil before use.
- the viscosity (8.178 cST) also was similar to that of the insulating oil before use (8.180 cST) . Further, it is found that irradiation of electron beam did not influence on other physical properties than specific gravity and viscosity.
- treating waste insulating oil by irradiating electron beam according to the present invention selectively removes PCBs contained in the waste insulating oil, and recovers the physical properties of the waste insulating oil to similar level of those of insulating oil before use.
- the present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil. According to the invention, only PCBs contained in waste insulating oil can be selectively removed by irradiating electron beam to the waste insulating oil, thereby effectively treating the waste insulating oil containing PCBs.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Lubricants (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The present invention relates to a method for processing waste insulating oil which contains polychlorinated biphenyls by irradiating electron beam to the waste insulating oil. More specifically, the invention is characterized in that electron beam of a certain range is irradiated to selectively remove only polychlorinated biphenyls contained in the waste insulating oil without any significant change for reuse if necessary.
Description
METHOD FOR PROCESSING WASTE INSULATING OIL WHICH CONTAINS POLYCHLORINATED BIPHENYLS USING ELECTRON-BEAM
[Technical Field]
The present invention relates to a method for processing waste insulating oil which contains polychlorinated biphenyls by irradiating electron beam to the waste insulating oil.
[Background Art]
A transformer used for a certain period cannot be used any more because of changed physical properties of insulating oil as a component of the transformer and decrease of durability of other constituents, so that the insulating oil and other constituents of the transformer are discarded. When insulating oil containing PCBS (POLYCHLORINATED BIPHENYLS) for enhancing the insulating effect is discarded, the problem is a possibility of generation of POPs (Persistent Organic Pollutants) such as dioxin, one of residual organic pollutant having high toxicity.
Polychlorinated biphenyls, in general, are compounds wherein hydrogen atoms bonded at ten hydrogen atom position of a biphenyl (C6H5-C6H5) are substituted by 1 ~ 10 chlorine atoms, having 242 kinds of isomers, theoretically. Among them, practically used are about 100 kinds. The polychlorinated
biphenyls are not decomposed by heat up to 300 deg C, insoluble in water and show excellent electric insulation, so that it has been widely used in electric products such as transformers and condensers. Polychlorinated biphenyls, when being flowed into a sewage discharge plant as it is after use, cause environmental disruption and change of ecosystem. Polychlorinated biphenyls had been used without any particular environmental measure, but later on, it was found as a serious pollutant, so that the production and use have been prohibited all over the world since 1976. However, 1 million ton of polychlorinated biphenyls has been already discharged into nature throughout the world, and the amount to be discarded reaches about 2 million ton. In Korea also, it is known that there is a large amount of polychlorinated biphenyls to be treated. Thus, a method for effectively decomposing polychlorinated biphenyls is urgently required.
According to US EPA, at least 90 kinds of techniques have been reported to treat polychlorinated biphenyls. Up to the present, biological processing techniques, physico-chemical processing techniques, thermal processing techniques or the like have been known as techniques for treating harmful chemicals such as polychlorinated biphenyls.
Biological processing using an enzyme, which is effective on treating polychlorinated biphenyls, is advantageous in that
it is applicable to various medium polluted by polychlorinated biphenyls, with generating minimum amount of residue. On the other hand, it is disadvantageous in that a long processing period is required, and the processing efficiency is largely affected by concentration of polychlorinated biphenyls.
Thermal processing technique represented by burning-up is advantageous in that the processing speed is high, and the volume of the waste treated is small. However, it is disadvantageous in that it is restrictive to be used for liquid or gaseous medium, relative high cost is required, and additional treatment of the residue generated is needed. In addition, when polychlorinated biphenyl containing product is burned in a common manner, it is reported that by-products such as polycyclic aromatic hydrocarbon including dioxin having higher toxicity than that of polychlorinated biphenyls, are produced. Thus, safe treatment of insulating oil containing polychlorinated biphenyls by means of burning is limited. In particular, as it has been known that dioxin being extremely harmful is generated and discharged, inhabitants of the region where an incinerator is to be established are strongly opposed to the establishment, thereby the material is frequently exported abroad for consigned treatment or storage for a long period. During long-term storage, polychlorinated biphenyls are liable to be discharged from the waste containing polychlorinated biphenyls to the environment,
thereby polluting the surroundings.
Thermo-chemical processing techniques, likewise thermal processing techniques, are disadvantageous in that additional treatment of the residue produced is required after the processing, while being advantageous in rapid processing speed and applicability to various medium polluted by polychlorinated biphenyls, as well as ability of treating high concentration of polychlorinated biphenyls to be utilized as a recycling technique. Commercialized chemical decomposition processes of polychlorinated biphenyls include metallic sodium dispersion process (Japan, Hokkaido) , dechlorinating decomposition process (Japan, Toyota) , alkaline catalyst decomposition process (US, Japan, Australia) , hydrogen- treatment dechlorination catalytic reaction (Japan, Osaka) , dechlorinating decomposition process (Japan, Kyushu, Canada) , hydrothermal oxidative decomposition (Japan, Tokyo) , organometallic alkaline decomposition (Japan) , chemical extraction decomposition (Japan) and ultra-critical water oxidation (US, Japan), or the like. Japanese Patent Laid- Open No. 1998-316798 describes a process for dechlorination by adding ethyl alcohol, ethylene glycol and alkaline hydroxide to an insulating oil containing polychlorinated biphenyls and irradiating ultraviolet ray in order to treat polychlorinated biphenyls contained in the insulating oil. Japanese Patent Laid-Open No. 2001-29942 describes a method to treat
polychlorinated biphenyls contained in the insulating oil by using titanium oxide as a photo-catalyst.
Decomposition process using ultraviolet ray has disadvantage of low decomposition efficiency. Chemical decomposition by use of an oxidant, though the decomposition can be completed in several hours, has problem of corrosion of the material of the device. Oxidative decomposition by using ultra-critical water is troublesome because of excessive energy consumption.
[Disclosure] [Technical Problem]
The object of the invention is to provide a process for treating waste insulating oil containing PCBs by irradiating electron beam to remove polychlorinated biphenyls (PCBs) contained in the waste insulating oil, maintaining the original properties of the treated oil.
[Technical Solution] The present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil. More specifically, it is characterized in that electron beam in a certain range is irradiated to selectively remove only PCBs contained in the waste insulating oil.
Transformers used for a certain period are discarded because of reduced electric performance. Waste transformers consisting of various expensive metals can be decomposed and reused as resources, while PCBs used in transformers to enhance insulating property are environmentally harmful with high toxicity to require much care in reuse and handling.
Now, specifically described is the process for treating waste insulating oil containing PCBs, according to the present invention. The present invention is characterized in that PCBs used in waste insulating oil containing PCBs in order to enhance insulating property of transformers are selectively removed, and electron beam is irradiated to the waste insulating oil containing PCBs to recover the physical properties of waste insulating oil to provide similar physical properties to initial insulating oil.
PCBs are compounds wherein hydrogens at ten hydrogen atom position of a biphenyl (C6H5-C6H5) are substituted by 1-10 chlorine atom(s), represented by following chemical formula. The chemical bonds between the biphenyl polycyclic aromatic compound and chloride ion are easily detached with low ionization energy because of very low chemical bonding energy between them.
In the chemical formula, m + n = 1 ~ 10.
The electron beam used according to the present invention is characterized in that it produces various kinds of chemical radicals (OH, 'H, e~, or the like) depending upon the ionization property , substances, and selectively decomposes chemical bonds in substances consisting of the chemical bonds.
The method for treating waste insulating oil containing
PCBs according to the present invention is to irradiating said electron beam in a range from 1 kGy to 10,000 kGy on the basis of absorbed dose to the waste insulating oil containing PCBs.
Preferably, only PCBs contained in the waste insulating oil are selectively removed when the electron beam is irradiated in a range from 40 kGy to 70 kGy on the basis of absorbed dose. When the electron beam is irradiated in a range from 20 kGy to
50 kGy on the basis of absorbed dose, viscosity, a physical property of waste insulating oil, can be reduced.
[Advantageous Effects] The present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil containing PCBs. According to the invention, only PCBs
contained in waste insulating oil can be selectively removed by irradiating electron beam to the waste insulating oil, thereby effectively treating the waste insulating oil containing PCBs.
[Description of Drawings]
Fig. 1 is a graph showing the change of concentration of polychlorinated biphenyls versus absorbed energy dose of electron beam. Fig. 2 is a graph showing the change of viscosity of waste insulating oil versus absorbed energy dose of electron beam.
[Mode for Invention] Other and further objects, features and advantages of the invention will appear more fully from the following description.
Examples [Example 1] Change of concentration of PCBs and viscosity depending on the absorbed energy dose of electron beam
To waste insulating oil containing PCBs, electron beam was irradiated in a dose of 10 kGy, 30 kGy, 50 kGy, 100 kGy and 150 kGy on the basis of absorbed dose, and the change of concentration of PCBs and that of viscosity depending on the
absorbed energy dose of electron beam were reported as graphs in Fig. 1 and Fig. 2, respectively.
The physical properties of the waste insulating oil before and after irradiation of electron beam, and physical properties of the insulating oil before use are shown in Table 1:
[Table 1]
Fig. 1 is a graph showing the change of concentration of PCBs contained in waste insulating oil, depending on the change of absorbed energy dose of electron beam. As shown in Fig. 1, the initial concentration of PCBs in the waste insulating oil was 112 mg/L (ppm) , which was higher by 100,000 folds than 0.001 ppm, the detection limit of PCBs'
concentration. The concentration of PCBs, 112 ppm, was abruptly reduced by irradiation of 30 JcGy of electron beam on the basis of absorbed dose. It was found that the whole quantity of PCBs was removed at the dose of 50 kGy or more. Such results were obtained because the chemical bonds between the biphenyl and chloride ion are selectively decomposed and detached by electron beam due to weak bonding energy between the polyaromatic biphenyl and chloride ion in PCBs.
Thus, it is found that the concentration of PCBs contained in waste insulating oil was reduced and completely removed by means of irradiation of electron beam, and the method is effective on decomposition of waste insulating oil containing PCBs.
Fig. 2 is a graph showing change of viscosity of waste insulating oil depending on the change of absorbed energy dose of electron beam. As shown in Fig. 2, the viscosity of waste insulating oil containing PCBs was 8.911 cST at 40°C, which was higher than the viscosity (8.180 cST) of insulating oil before use. The change of viscosity is found to be caused by change of physical properties of insulation oil resulted from use of the transformer for a long period. The viscosity of the waste insulating oil having 8.911 cST of viscosity was reduced to the viscosity of the insulating oil before use, by irradiation of 30 kGy of electron beam on the basis of absorbed dose. With increasing the irradiation dose of electron beam, the
viscosity of the waste insulating oil was slowly decreased.
Therefore, it is found that the viscosity can be tailored as required by irradiating electron beam in an appropriate range on the basis of absorbed dose. Table 1 shows change of physical properties when the waste insulating oil containing PCBs that had been treated by irradiating electron beam according to the present invention was reused in a transformer. It is found that pour point, refractive index, viscosity gravity constant and refractive index intercept of the waste insulating oil were same as those of the insulating oil before use, with only the specific gravity and viscosity being changed.
Waste insulating oil before irradiating electron beam had specific gravity of 0.861, that was significantly higher than that of insulating oil before use, but the waste insulating oil containing PCBs, after treating by irradiation of electron beam, had specific gravity of 0.839 that is similar to that of insulating oil before use. The viscosity (8.178 cST) also was similar to that of the insulating oil before use (8.180 cST) . Further, it is found that irradiation of electron beam did not influence on other physical properties than specific gravity and viscosity.
Thus, it was found that treating waste insulating oil by irradiating electron beam according to the present invention selectively removes PCBs contained in the waste insulating oil,
and recovers the physical properties of the waste insulating oil to similar level of those of insulating oil before use.
[industrial Applicability] The present invention relates to a process for treating waste insulating oil containing PCBs, which is characterized by irradiating electron beam to the waste insulating oil. According to the invention, only PCBs contained in waste insulating oil can be selectively removed by irradiating electron beam to the waste insulating oil, thereby effectively treating the waste insulating oil containing PCBs.
Claims
[CLAIMS] [Claim l]
A method for processing waste insulating oil which contains polychlorinated biphenyls (PCBs) , by irradiating electron beam to the waste insulating oil. [Claim 2]
A method for processing waste insulating oil which contains polychlorinated biphenyls according to claim 1, wherein said electron beam is irradiated in a range from 1 kGy to 10,000 kGy on the basis of absorbed dose. [Claim 3]
A method for processing waste insulating oil which contains polychlorinated biphenyls according to claim 2, wherein said electron beam is irradiated in a range from 40 kGy to 70 kGy on the basis of absorbed dose to selectively remove only polychlorinated biphenyls contained in the waste insulating oil. [Claim 4]
A method for processing waste insulating oil which contains polychlorinated biphenyls according to claim 2, wherein said electron beam is irradiated in a range from 20 kGy to 50 kGy on the basis of absorbed dose to reduce the viscosity of the waste insulating oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2006-0007729 | 2006-01-25 | ||
| KR1020060007729A KR100653960B1 (en) | 2006-01-25 | 2006-01-25 | Method for processing waste insulating oil which contains polychlorinated biphenyls using electron-beam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007086667A1 true WO2007086667A1 (en) | 2007-08-02 |
Family
ID=37732099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2007/000380 WO2007086667A1 (en) | 2006-01-25 | 2007-01-23 | Method for processing waste insulating oil which contains polychlorinated biphenyls using electron-beam |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100653960B1 (en) |
| WO (1) | WO2007086667A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100798410B1 (en) | 2007-03-14 | 2008-01-28 | 한국원자력연구원 | A method of eliminating chlorine element in waste insulating oil |
| KR100969548B1 (en) | 2009-08-07 | 2010-07-12 | 송병주 | Biphenyl decomposition system of polychlorinated |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4864811A (en) * | 1987-09-21 | 1989-09-12 | Pfefferle William C | Method for destroying hazardous organics |
| US5062372A (en) * | 1989-12-20 | 1991-11-05 | Ritter Robert A | Lined hazardous waste incinerator |
| US5541386A (en) * | 1991-01-24 | 1996-07-30 | Irm, L.P. | Plasma arc decomposition of hazardous wastes into vitrified solids and non-hazardous gasses |
| US5648591A (en) * | 1992-12-18 | 1997-07-15 | University Of Western Australia | Toxic material disposal |
-
2006
- 2006-01-25 KR KR1020060007729A patent/KR100653960B1/en active IP Right Grant
-
2007
- 2007-01-23 WO PCT/KR2007/000380 patent/WO2007086667A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4864811A (en) * | 1987-09-21 | 1989-09-12 | Pfefferle William C | Method for destroying hazardous organics |
| US5062372A (en) * | 1989-12-20 | 1991-11-05 | Ritter Robert A | Lined hazardous waste incinerator |
| US5541386A (en) * | 1991-01-24 | 1996-07-30 | Irm, L.P. | Plasma arc decomposition of hazardous wastes into vitrified solids and non-hazardous gasses |
| US5648591A (en) * | 1992-12-18 | 1997-07-15 | University Of Western Australia | Toxic material disposal |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100653960B1 (en) | 2006-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Enhanced removal of methylparaben mediated by cobalt/carbon nanotubes (Co/CNTs) activated peroxymonosulfate in chloride-containing water: Reaction kinetics, mechanisms and pathways | |
| Cheng et al. | Hydroxyl radicals based advanced oxidation processes (AOPs) for remediation of soils contaminated with organic compounds: a review | |
| Hashmi et al. | Chemical remediation and advanced oxidation process of polychlorinated biphenyls in contaminated soils: a review | |
| Daraei et al. | Study on the biodegradability improvement of 2, 4 dinitrophenol in wastewater using advanced oxidation/reduction process with UV/SO3/ZnO | |
| Ikhlaq et al. | Solar Photo-Catalytic ozonation on γ-alumina for the removal of dyes in wastewater | |
| WO2007086667A1 (en) | Method for processing waste insulating oil which contains polychlorinated biphenyls using electron-beam | |
| KR101571516B1 (en) | Persulfate activation using zero-valent iron and soil-groundwater remediation by the activation | |
| CN107381770B (en) | Water treatment method for activating hydrogen peroxide under neutral condition | |
| Akhondi et al. | Base-catalysed decomposition of polychlorinated biphenyls in transformer oils by mixture of sodium hydroxide, glycerol and iron | |
| Endo et al. | Hydrothermal alkaline defluorination rate of perfluorocarboxylic acids (PFCAs) | |
| JP4804495B2 (en) | Method for treating cleaning wastewater containing chlorine-containing organic compounds | |
| KR101021690B1 (en) | Method for treatment of wasted insulation oil including polychlorinated biphenyls | |
| Kargar et al. | Kinetics of degradation of perchloroethylene under ultrasonic irradiation and photooxidation in aqueous solution | |
| JP2003311231A (en) | Cleaning method and cleaning apparatus | |
| JP2006296694A (en) | Decomposition method of halogenated organic compound | |
| Olasupo et al. | Trends in low temperature and non-thermal technologies for the degradation of persistent organic pollutants | |
| Chen | PFAS Characteristics and Treatment for Landfill Leachate | |
| Sil et al. | Strategies for mitigation of polychlorinated biphenyls (PCBs): A review | |
| Lee et al. | Remediation of Dioxins-Contaminated Soil by Successive Ethanol Washing–Photodegradation | |
| KR102603247B1 (en) | A polychloride biphenyl elimination system and its operation method | |
| KR100798410B1 (en) | A method of eliminating chlorine element in waste insulating oil | |
| JP2004313932A (en) | Method for cleaning wastewater containing harmful organic matter | |
| Liu | Enhanced photocatalytic oxidation of polycyclic aromatic hydrocarbons in offshore produced water | |
| KR100969548B1 (en) | Biphenyl decomposition system of polychlorinated | |
| Zolekafeli et al. | PHOTOCATALYTIC PERFORMANCE OF MOLYBDENUM DISULPHIDE-GRAPHENE OXIDE IN PERFLUOROOCTANOIC ACID (PFOA) DEGRADATION UNDER INDOOR LIGHT EMITTING DIODE (LED) IRRADIATION |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 07708561 Country of ref document: EP Kind code of ref document: A1 |