CA2001880A1 - Process for removing liquid containing chlorinated organic compounds from liquide-impregnated components of appliance and apparatus for carrying out said process - Google Patents
Process for removing liquid containing chlorinated organic compounds from liquide-impregnated components of appliance and apparatus for carrying out said processInfo
- Publication number
- CA2001880A1 CA2001880A1 CA 2001880 CA2001880A CA2001880A1 CA 2001880 A1 CA2001880 A1 CA 2001880A1 CA 2001880 CA2001880 CA 2001880 CA 2001880 A CA2001880 A CA 2001880A CA 2001880 A1 CA2001880 A1 CA 2001880A1
- Authority
- CA
- Canada
- Prior art keywords
- alkaline earth
- alkali
- components
- liquid
- reactant
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 58
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 title claims description 8
- 239000003513 alkali Substances 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 16
- 150000001805 chlorine compounds Chemical class 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010943 off-gassing Methods 0.000 claims 3
- 239000000843 powder Substances 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 abstract description 5
- -1 for example Chemical class 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract 1
- 239000000306 component Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 8
- 150000004074 biphenyls Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 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 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 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 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004029 environmental poison Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/08—Cooling; Ventilating
- H01F27/10—Liquid cooling
- H01F27/12—Oil cooling
- H01F27/14—Expansion chambers; Oil conservators; Gas cushions; Arrangements for purifying, drying, or filling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/006—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents of waste oils, e.g. PCB's containing oils
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Biomedical Technology (AREA)
- Processing Of Solid Wastes (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The process is intended to remove chlorinated organic compounds such as, for example, PCBs from very inaccessible components (core 3) of appliances which contain, like transformers, such compounds as oil fill-ing, in an inexpensive and nevertheless environmentally compatible manner.
This is achieved by releasing the chlorine-containing compounds in the presence of a reactant which binds the chlorine in the form of an alkali chloride and/or alkaline earth chloride. The metallic components of the appliances are consequently accessible for a re-cycling process in an extremely environmentally compatible and economic manner.
Fig. 1
The process is intended to remove chlorinated organic compounds such as, for example, PCBs from very inaccessible components (core 3) of appliances which contain, like transformers, such compounds as oil fill-ing, in an inexpensive and nevertheless environmentally compatible manner.
This is achieved by releasing the chlorine-containing compounds in the presence of a reactant which binds the chlorine in the form of an alkali chloride and/or alkaline earth chloride. The metallic components of the appliances are consequently accessible for a re-cycling process in an extremely environmentally compatible and economic manner.
Fig. 1
Description
zn~
Ka/eh 31.10.88 88/106 Modified Version for Foreign Applications (4.8.89) S TITLE OF THE INVENTION
Process for removing liquid containing chlorinated organic compounds from liquid-impregnated components of an appliance and apparatus for carrying out said process.
BACKGROUND OF THE INVENTION
Field of the Invention The invention is based on a process as defined in the preamble of Patent claim 1. The invention relates also to apparatuses for carrying out the process.
Discussion of Back~round A process of the type mentioned in the intro-duction is disclosed, for example, by D~-A-2,756,298 and US-A-4,6~9,667. The known process is intended to remove from transfor~ers the residual polychlorinated biphenyls remaining in very inaccessible components such as, for instance, organic insulating materials based on wood, paper, cotton-or plastic, after insulating liquid based on polychlorinated biphenyls tPCB) has been drained. For this purpose, the components impregnated with the biph-enyls are treated with the vapour of a solvent such as water or methanol in an autoclave at elevated temper-atures and a gaseous azeotropic mixture of solvent and biphenyls then produced is discharged from the autoclave and cooled to for~ a li~uid containing the residual biphenyls. The biphenyls from this liquid are then destroyed, preferably by irradiation with W light or by adding ozone. Depending on the solvent used, the biph-enyls may, however, also be destroyed by adding metallic sodium. The dissolution and discharge cycle described above has to be repeated several times in order to removP
the biphenyls from the biphenyl-impregnated components at znn~
least in a fairly satisfactory manner. Such a process i5 therefore extremely lengthy. In addition the biphenyls cannot be completely removed thereby. In particular, as a result of the desiqn of the components, even vaporous S solvent can frequently not reach all the points of the biphenyl-impregnated components.
To remove polychlorinated biphenyls from trans-formers, it is further suggested to comminute the entire transformer by shredding and then to treat the shredded material thereby formed with solvent. Metal parts are thereupon separated from organic constituents. Such a process requires, however, numerous technologically demanding process steps and is therefore relatively expensive.
A further proposal relates to a pyrolysis process in which the transformer core, which is impregnated with insulating oil, is heated in a pyrolysis furnace with air excluded. Organic components impregnated with chlorinated biphenyls are thereby pyrolytically decomposed and burnt in an afterburner. In this process, however, undecomposed chlorinated biphenyl may reach the afterburner, at least in the heating-up phase as a result of which the risk of dioxin formation cannot be eliminated.
SUMM~RY OF THE I~VENTION
Accordingly, one object of this invention as it is defined in patent claims 1, 8, 9 and 10, is to achieve the object of providing a process and apparatuses for carrying out the said process which make it possible to dispose of components, impregnated with chlorinated organic compounds, of any appliance in a comparatively short time and with comparatively simple, and, con-sequently, operationally reliable technology.
The process and the apparatuses as claimed by the invention are outstanding for the fact that it is possible to render harmless, rapidly and without risk, very inaccessible environmental poisons in process steps which are technologically simple to carry out, such as thermal release of the chlorinated organic compounds, "~:
Ka/eh 31.10.88 88/106 Modified Version for Foreign Applications (4.8.89) S TITLE OF THE INVENTION
Process for removing liquid containing chlorinated organic compounds from liquid-impregnated components of an appliance and apparatus for carrying out said process.
BACKGROUND OF THE INVENTION
Field of the Invention The invention is based on a process as defined in the preamble of Patent claim 1. The invention relates also to apparatuses for carrying out the process.
Discussion of Back~round A process of the type mentioned in the intro-duction is disclosed, for example, by D~-A-2,756,298 and US-A-4,6~9,667. The known process is intended to remove from transfor~ers the residual polychlorinated biphenyls remaining in very inaccessible components such as, for instance, organic insulating materials based on wood, paper, cotton-or plastic, after insulating liquid based on polychlorinated biphenyls tPCB) has been drained. For this purpose, the components impregnated with the biph-enyls are treated with the vapour of a solvent such as water or methanol in an autoclave at elevated temper-atures and a gaseous azeotropic mixture of solvent and biphenyls then produced is discharged from the autoclave and cooled to for~ a li~uid containing the residual biphenyls. The biphenyls from this liquid are then destroyed, preferably by irradiation with W light or by adding ozone. Depending on the solvent used, the biph-enyls may, however, also be destroyed by adding metallic sodium. The dissolution and discharge cycle described above has to be repeated several times in order to removP
the biphenyls from the biphenyl-impregnated components at znn~
least in a fairly satisfactory manner. Such a process i5 therefore extremely lengthy. In addition the biphenyls cannot be completely removed thereby. In particular, as a result of the desiqn of the components, even vaporous S solvent can frequently not reach all the points of the biphenyl-impregnated components.
To remove polychlorinated biphenyls from trans-formers, it is further suggested to comminute the entire transformer by shredding and then to treat the shredded material thereby formed with solvent. Metal parts are thereupon separated from organic constituents. Such a process requires, however, numerous technologically demanding process steps and is therefore relatively expensive.
A further proposal relates to a pyrolysis process in which the transformer core, which is impregnated with insulating oil, is heated in a pyrolysis furnace with air excluded. Organic components impregnated with chlorinated biphenyls are thereby pyrolytically decomposed and burnt in an afterburner. In this process, however, undecomposed chlorinated biphenyl may reach the afterburner, at least in the heating-up phase as a result of which the risk of dioxin formation cannot be eliminated.
SUMM~RY OF THE I~VENTION
Accordingly, one object of this invention as it is defined in patent claims 1, 8, 9 and 10, is to achieve the object of providing a process and apparatuses for carrying out the said process which make it possible to dispose of components, impregnated with chlorinated organic compounds, of any appliance in a comparatively short time and with comparatively simple, and, con-sequently, operationally reliable technology.
The process and the apparatuses as claimed by the invention are outstanding for the fact that it is possible to render harmless, rapidly and without risk, very inaccessible environmental poisons in process steps which are technologically simple to carry out, such as thermal release of the chlorinated organic compounds, "~:
2()~
with at least partial decomposition of the appliance components to be disposed of and trapping of the chlorine from the compounds released with a reactant yielding alkali chlorides and/or alkaline earth chlorides.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
Fig. 1 shows an apparatus for carrying out the process according to the invention in which the com-ponents to be disposed of are treated in an aqueous, sodium-containing solution, Fig. 2 shows an apparatus for carrying out the process according to the invention in which the com-ponents to be disposed of are outgassed and the chlorine-containing process gas then produced is washed out in an aqueous solution of sodium hydroxide, and Fig. 3 shows an apparatus for carrying ou~ the process according to the invention in which the com-ponents to be disposed of are outgassed and the chlorine-containing process gas then produced is passed through a melt of sodium hydroxide.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, in the apparatus shown in Figure 1, 1 denotes an au~oclave having a heating system 2 with a pressure monitoring system P and a temperature monitoring system T. The interior of the autoclave contains a core 3 of a transformer filled with an insulating oil, for instance, based on polychlorinated biphenyls and~or trichlorobenzine. After the insulating oil has been drained, the core 3 contains the residual ., insulating oil remaining in the very inaccessible pores of its organic components. In a 630 kV transformer containing, for example, 40 kg of organic components comprising, for example, wood, paper, cotton and/or plastic, and about 400 kg of insulating oil, the mass of this residual oil may be approx. 10 kg. An aqueous sol-ution containing alkali and/or alkaline earth and sub-jected to a pressure of 5-50, preferably 10-20, bar is fed to the autoclave 1 via a pump 4. This solution preferably contains hydroxide~ of the alkali metals of alkaline earth metals and may be, for instance, a 10%-strength sodium hydroxide solution. The solution may, however, also contain salts of the alkali metals and alkaline earth metals such as, for instance, sodium sulphate or sodium carbonate.
At temperatures between approx. 200 and 300, preferably 220 and 280, C, the organic components of the core 3 dissolve after a few hours and the chlorinated organic compound~ are released even from very inacces-sible pores, partly with decomposition and possibly withdetachment of chlorine. The ionised alkali and/or alkaline earth contained in the solution reacts with the partially still organically bound chlorine or even chlorine present in the form of hydrochloric acid to form alkali chloride and/or alkaline earth chloride. After the treatment, which lasts only a few hours, a vapour stream enriched with alkali chlorides and/or alkaline earth chlorides, hydrocarbons and aqueous alkali starting solution and/or alkaline earth starting solution may be drawn off via a reducing valve 5 and fed to a storage tank 6. The hydrocarbons deposit therein as an easily removable layer 7 on the surface of the remaining un-treated water 8. The untreated water 8 may then be depleted of remaining hydrocarbons and alkali chlorides and/or alkaline earth chlorides, for instance, by wet oxidation, ozone/ W treat~ent, distillation, desalination or biological treatment in a water processor 9. It may thereupon be removed or transferred again to the process described in order to process the aqueous alkali solution ZO('~ O
and/or al~aline earth solution.
When all the components of the core 3 Lmpregnated with insulating oil have been dissolved after several hours, the autoclave 1, which is free of insulating oil S but possibly contains residues of the components which are still undissolved but free of insulating oil, as well as residues of the solvent, is washed out with pure water vapour. After cooling, the core 3 may then be removed from the autoclave and is free of chlorinated organic compounds.
Instead of a transformer core, components, impregnated with insulating oil, of other electrical appliances, for example high-voltage capacitors, or any other appliances containing components which are impreg-lS nated with chlorinated organic compounds, can also be disposed of in a corresponding manner.
In the embodiments of apparatuses for carrying out the process according to the invention shown in Figures 2 and 3, reference symbols corresponding to Figure 1 relate to parts functioning in accordance with Figure 1. In the apparatus according to Figure 2 the autoclave 1 is used to outgas the core 3 Lmpregnated with insulating oil. The organic components of the core 3 impregnated with insulating oil are outgassed by heating to approx. 300-600C, preferably 350-450C, with an inert carrier gas such as nitrogen being supplied, with partial decomposition. The process gas thereby formed containing chlorinated and chlorine-free organic compounds, water, hydrogen chloride and nitrogen is fed into a gas scrubber 10 heated to approx. 200-300C. Liquid is forced into the gas scrubber 10 from a storage container 11 filled with an aqueous alkali solution and/or alkaline earth solu-tion, for example, with 10~-strength sodium hydroxide solution, at a pressure between 0.5 and 10 bar. In this process, the chlorine contained in the process gas predominantly in the form of hydrogen chloride gas, po~sibly, however, also still in the for~ of chlorinated orsanic hydrocarbons, for instance as PCB, becomes bound to form alkali chlorides and/or alkaline earth chlorides.
~0~
The vapour emerging from the gas scrubber 10 via an overflow valve 12 contains, in addition to excess alkali solution and/or alkaline earth solution, water and alkali chlorides and/or alkaline earth chlorides, only unchlorinated organic compounds and some carbon dioxide.
The discharged vapour is condensed in a condenser 13 and the liquid condensate formed in the condenser is fed into the storage tank 6 in which, similarly to the apparatus according to Figure 1, the layer 7 formed from chlorine-free hydrocarbons is removed from the surface of the untreated water 8 and the untreated water is fed into the water processor 9 for further treatment. In this process it may be advantageous to remove any solid particles contained in the untreated water and produced in the process described abo~e by means of a filter 14 fitted between storage tank 6 and water processor 9. The carrier gas fed into the storage tank 6 is fed back into the autoclave 1, optionally via an analytichl apparatus 15 which examines its components and a pump 16.
The process according to Figure 2 has the additional advantage that fresh alkali or alkaline earth is always introduced into the gas scrubber 10. This reliably achieves the result that any chlorinated hydro-carbons still contained in the process gas and introduced into the gas scrubber 10 are dechlorinated to form alkali chloride or alkaline earth chloride. In addition, this process is outstanding for a high flow rate, accompanied by high operating reliability.
Similarly to the apparatus according to Figure 2, process gas containing predominantly chlorine-free organic compounds, hydrogenchloride, water and nitrogen is formed in the apparatus according to Figure 3. The process gas is fed into a heatable reactor 17. This reactor contains a melt 18 containing alkali and/or alkaline earth. If a sodium hydroxide melt is used, it is heated to approx. 400C. The process gas is fed into regions of the melt 18 near the base. As the process gas rises, the chlorine contained in the process gas becomes bound as alkali chloride and/or alkaline earth chloride.
O
The remaining parts of the process ~as, such as chlorine-free organic compounds and also proportions of carbondioxide and water, are fed into the condenser 13.
The condensate formed during this operation reaches the storage tank 6. After examination for organic chlorine compounds in the analytical apparatus 15, incondensable organic hydrocarbons are fed to a combustion apparatus l9. After the condensates formed have been demonstrated to be safe, the liquid portion 20 of the condensate may also be fed to this combustion apparatus. Instead of a melt, a porous solid or granular material, for instance based on calcium oxide/silicon dioxide, containing alkali and/or alkaline earth may be used.
The reaction products produced can be monitored in a particularly simple manner for freedom from chlorine and disposed of both if a reactant of this type is used and also if a melt is used as reactant. In addition, the pressure can be set both in the autoclave 1 and also in the reactor 17 in any desired manner, for instance by means of a pump 21 fitted downstream of the condenser 13.
If the pump 21 is fitted, the connecting pipe indicated in Figure 3 between storage tank 6 and analytical apparatus 15 is omitted. By means of an operating procedure employing underpressure, it is thus possible, in a simple manner, to achieve the result that chlorin-ated hydrocarbons definitely do not escape to the outside from the apparatus during the process.
Obviously, numerous modifications and variations of the present invention are possible in the light of the above teaching. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
Fig. 1 shows an apparatus for carrying out the process according to the invention in which the com-ponents to be disposed of are treated in an aqueous, sodium-containing solution, Fig. 2 shows an apparatus for carrying out the process according to the invention in which the com-ponents to be disposed of are outgassed and the chlorine-containing process gas then produced is washed out in an aqueous solution of sodium hydroxide, and Fig. 3 shows an apparatus for carrying ou~ the process according to the invention in which the com-ponents to be disposed of are outgassed and the chlorine-containing process gas then produced is passed through a melt of sodium hydroxide.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, in the apparatus shown in Figure 1, 1 denotes an au~oclave having a heating system 2 with a pressure monitoring system P and a temperature monitoring system T. The interior of the autoclave contains a core 3 of a transformer filled with an insulating oil, for instance, based on polychlorinated biphenyls and~or trichlorobenzine. After the insulating oil has been drained, the core 3 contains the residual ., insulating oil remaining in the very inaccessible pores of its organic components. In a 630 kV transformer containing, for example, 40 kg of organic components comprising, for example, wood, paper, cotton and/or plastic, and about 400 kg of insulating oil, the mass of this residual oil may be approx. 10 kg. An aqueous sol-ution containing alkali and/or alkaline earth and sub-jected to a pressure of 5-50, preferably 10-20, bar is fed to the autoclave 1 via a pump 4. This solution preferably contains hydroxide~ of the alkali metals of alkaline earth metals and may be, for instance, a 10%-strength sodium hydroxide solution. The solution may, however, also contain salts of the alkali metals and alkaline earth metals such as, for instance, sodium sulphate or sodium carbonate.
At temperatures between approx. 200 and 300, preferably 220 and 280, C, the organic components of the core 3 dissolve after a few hours and the chlorinated organic compound~ are released even from very inacces-sible pores, partly with decomposition and possibly withdetachment of chlorine. The ionised alkali and/or alkaline earth contained in the solution reacts with the partially still organically bound chlorine or even chlorine present in the form of hydrochloric acid to form alkali chloride and/or alkaline earth chloride. After the treatment, which lasts only a few hours, a vapour stream enriched with alkali chlorides and/or alkaline earth chlorides, hydrocarbons and aqueous alkali starting solution and/or alkaline earth starting solution may be drawn off via a reducing valve 5 and fed to a storage tank 6. The hydrocarbons deposit therein as an easily removable layer 7 on the surface of the remaining un-treated water 8. The untreated water 8 may then be depleted of remaining hydrocarbons and alkali chlorides and/or alkaline earth chlorides, for instance, by wet oxidation, ozone/ W treat~ent, distillation, desalination or biological treatment in a water processor 9. It may thereupon be removed or transferred again to the process described in order to process the aqueous alkali solution ZO('~ O
and/or al~aline earth solution.
When all the components of the core 3 Lmpregnated with insulating oil have been dissolved after several hours, the autoclave 1, which is free of insulating oil S but possibly contains residues of the components which are still undissolved but free of insulating oil, as well as residues of the solvent, is washed out with pure water vapour. After cooling, the core 3 may then be removed from the autoclave and is free of chlorinated organic compounds.
Instead of a transformer core, components, impregnated with insulating oil, of other electrical appliances, for example high-voltage capacitors, or any other appliances containing components which are impreg-lS nated with chlorinated organic compounds, can also be disposed of in a corresponding manner.
In the embodiments of apparatuses for carrying out the process according to the invention shown in Figures 2 and 3, reference symbols corresponding to Figure 1 relate to parts functioning in accordance with Figure 1. In the apparatus according to Figure 2 the autoclave 1 is used to outgas the core 3 Lmpregnated with insulating oil. The organic components of the core 3 impregnated with insulating oil are outgassed by heating to approx. 300-600C, preferably 350-450C, with an inert carrier gas such as nitrogen being supplied, with partial decomposition. The process gas thereby formed containing chlorinated and chlorine-free organic compounds, water, hydrogen chloride and nitrogen is fed into a gas scrubber 10 heated to approx. 200-300C. Liquid is forced into the gas scrubber 10 from a storage container 11 filled with an aqueous alkali solution and/or alkaline earth solu-tion, for example, with 10~-strength sodium hydroxide solution, at a pressure between 0.5 and 10 bar. In this process, the chlorine contained in the process gas predominantly in the form of hydrogen chloride gas, po~sibly, however, also still in the for~ of chlorinated orsanic hydrocarbons, for instance as PCB, becomes bound to form alkali chlorides and/or alkaline earth chlorides.
~0~
The vapour emerging from the gas scrubber 10 via an overflow valve 12 contains, in addition to excess alkali solution and/or alkaline earth solution, water and alkali chlorides and/or alkaline earth chlorides, only unchlorinated organic compounds and some carbon dioxide.
The discharged vapour is condensed in a condenser 13 and the liquid condensate formed in the condenser is fed into the storage tank 6 in which, similarly to the apparatus according to Figure 1, the layer 7 formed from chlorine-free hydrocarbons is removed from the surface of the untreated water 8 and the untreated water is fed into the water processor 9 for further treatment. In this process it may be advantageous to remove any solid particles contained in the untreated water and produced in the process described abo~e by means of a filter 14 fitted between storage tank 6 and water processor 9. The carrier gas fed into the storage tank 6 is fed back into the autoclave 1, optionally via an analytichl apparatus 15 which examines its components and a pump 16.
The process according to Figure 2 has the additional advantage that fresh alkali or alkaline earth is always introduced into the gas scrubber 10. This reliably achieves the result that any chlorinated hydro-carbons still contained in the process gas and introduced into the gas scrubber 10 are dechlorinated to form alkali chloride or alkaline earth chloride. In addition, this process is outstanding for a high flow rate, accompanied by high operating reliability.
Similarly to the apparatus according to Figure 2, process gas containing predominantly chlorine-free organic compounds, hydrogenchloride, water and nitrogen is formed in the apparatus according to Figure 3. The process gas is fed into a heatable reactor 17. This reactor contains a melt 18 containing alkali and/or alkaline earth. If a sodium hydroxide melt is used, it is heated to approx. 400C. The process gas is fed into regions of the melt 18 near the base. As the process gas rises, the chlorine contained in the process gas becomes bound as alkali chloride and/or alkaline earth chloride.
O
The remaining parts of the process ~as, such as chlorine-free organic compounds and also proportions of carbondioxide and water, are fed into the condenser 13.
The condensate formed during this operation reaches the storage tank 6. After examination for organic chlorine compounds in the analytical apparatus 15, incondensable organic hydrocarbons are fed to a combustion apparatus l9. After the condensates formed have been demonstrated to be safe, the liquid portion 20 of the condensate may also be fed to this combustion apparatus. Instead of a melt, a porous solid or granular material, for instance based on calcium oxide/silicon dioxide, containing alkali and/or alkaline earth may be used.
The reaction products produced can be monitored in a particularly simple manner for freedom from chlorine and disposed of both if a reactant of this type is used and also if a melt is used as reactant. In addition, the pressure can be set both in the autoclave 1 and also in the reactor 17 in any desired manner, for instance by means of a pump 21 fitted downstream of the condenser 13.
If the pump 21 is fitted, the connecting pipe indicated in Figure 3 between storage tank 6 and analytical apparatus 15 is omitted. By means of an operating procedure employing underpressure, it is thus possible, in a simple manner, to achieve the result that chlorin-ated hydrocarbons definitely do not escape to the outside from the apparatus during the process.
Obviously, numerous modifications and variations of the present invention are possible in the light of the above teaching. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
Claims (11)
1. A process for removing liquid containing chlorinated organic compounds from an appliance by heat treat-ment of liquid-impregnated components of said appliance, which comprises at least partially decomposing the liquid-impregnated components during the heat treatment and releasing a process product which contains at least hydrogen chloride and chlorinated organic compounds and which is fed at elevated temperatures to a reactant which forms alkali chloride and/or alkaline earth chloride.
2. The process as claimed in claim 1, wherein the reactant is an aqueous solution containing alkali and/or alkaline earth which at least partially decomposes the liquid-impregnated components at elevated temperatures.
3. The process as claimed in claim 1, wherein the chlorine compounds are released by outgassing, and wherein the process gas thereby formed is scrubbed with an aqueous solution containing alkali and/or alkaline earth as reactant.
4. The process as claimed in claim 1, wherein the chlorine compounds are released by outgassing, and wherein the process gas thereby formed is fed through a melt containing alkali and/or alkaline earth as reactant.
5. The process as claimed in claims 2 to 4, wherein the alkali and/or alkaline earth is used in the form of a hydroxide.
6. The process as claimed in claim 1, wherein the chlorine compounds are released by outgassing, and wherein the process gas thereby formed is fed through a solid containing alkali and/or alkaline earth as reactant or formed from powder or granular material.
7. The process as claimed in one of claLms 4 to 6, wherein the process gas is kept at underpressure.
8. An apparatus for carrying out the process as claimed in claim 1, which comprises an autoclave (1) which receives the liquid-impregnated components and is filled with a solution which contains alkali and/or alkaline earth and which at least partially decomposes said components.
9. An apparatus for carrying out the process as claimed in claim 1, which comprises an autoclave (1) which receives the liquid-impregnated components and produces process gas which contains compounds containing chlorine, and a reactor which is con-nected downstream of the autoclave (1) and contains alkali and/or alkaline earth and which is heated to temperatures which promote the formation of alkali chloride and/or alkaline earth chloride from the process gas supplied and the alkali and/or alkaline earth.
10. The apparatus as claimed in claim 9, wherein the reactor is a gas scrubber (10) having an apparatus for introducing a solution containing alkali and/or alkaline earth.
11. The apparatus as claimed in claim 9, wherein the reactor contains a melt containing alkali and/or alkaline earth, a porous solid body containing alkali and/or alkaline earth, or a powder or granular material containing alkali and/or alkaline earth.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4044/88-2 | 1988-10-31 | ||
| CH4044/88A CH676084A5 (en) | 1988-10-31 | 1988-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2001880A1 true CA2001880A1 (en) | 1990-04-30 |
Family
ID=4268770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2001880 Abandoned CA2001880A1 (en) | 1988-10-31 | 1989-10-31 | Process for removing liquid containing chlorinated organic compounds from liquide-impregnated components of appliance and apparatus for carrying out said process |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0371239A1 (en) |
| CA (1) | CA2001880A1 (en) |
| CH (1) | CH676084A5 (en) |
| DK (1) | DK542389A (en) |
| NO (1) | NO894315L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO308831B1 (en) * | 1995-03-22 | 2000-11-06 | Nkt Res Ct As | Process for the treatment of halogen-containing waste material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301137A (en) * | 1977-12-21 | 1981-11-17 | Occidental Research Corporation | Removal of chlorine from pyrolysis vapors |
| US4425949A (en) * | 1981-02-03 | 1984-01-17 | Diamond Shamrock Corporation | Process for removing undesirable substances from electrical devices |
| IT1157287B (en) * | 1982-07-02 | 1987-02-11 | Vittorio Colombini | PROCEDURE FOR THE POLLUTION OF ELECTRICAL-MECHANICAL EQUIPMENT FROM POLY-CHLORINE-DIPHENYL |
| US4699667A (en) * | 1983-11-14 | 1987-10-13 | Westinghouse Electric Corp. | Removing residual PCB S from transformers |
| DE3520671A1 (en) * | 1985-06-08 | 1986-12-11 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | METHOD FOR PURIFYING HOT EXHAUST GAS |
| DE3615027A1 (en) * | 1986-05-02 | 1987-11-05 | Dietrich Dipl Ing Dr Radke | Process for destroying organic halogen compounds, in particular chlorinated biphenyls, polychlorinated dioxins and polychlorinated furans |
| CA1268618A (en) * | 1986-11-05 | 1990-05-08 | William P. Trumble | Method for making an optical waveguide element |
-
1988
- 1988-10-31 CH CH4044/88A patent/CH676084A5/de not_active IP Right Cessation
-
1989
- 1989-10-14 EP EP89119117A patent/EP0371239A1/en not_active Withdrawn
- 1989-10-30 NO NO89894315A patent/NO894315L/en unknown
- 1989-10-31 CA CA 2001880 patent/CA2001880A1/en not_active Abandoned
- 1989-10-31 DK DK542389A patent/DK542389A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DK542389D0 (en) | 1989-10-31 |
| EP0371239A1 (en) | 1990-06-06 |
| DK542389A (en) | 1990-05-01 |
| NO894315L (en) | 1990-05-02 |
| NO894315D0 (en) | 1989-10-30 |
| CH676084A5 (en) | 1990-12-14 |
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