EP2024038B1 - Verfahren zur regenerierung von altöl - Google Patents

Verfahren zur regenerierung von altöl Download PDF

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Publication number
EP2024038B1
EP2024038B1 EP07748485.5A EP07748485A EP2024038B1 EP 2024038 B1 EP2024038 B1 EP 2024038B1 EP 07748485 A EP07748485 A EP 07748485A EP 2024038 B1 EP2024038 B1 EP 2024038B1
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Prior art keywords
oil
transformer
hydrogen
gas phase
separator
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English (en)
French (fr)
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EP2024038A1 (de
EP2024038A4 (de
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Björn HARRYSSON
Ahmad Kalantar
Gunnar Stang
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Nynas AB
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Nynas AB
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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

Definitions

  • the present invention relates to a process for the regeneration of a used oil. More particularly, the present invention relates to a process for the regeneration of a used oil, in particular a used transformer oil, by catalytic hydrogenation at an elevated pressure and at an elevated temperature.
  • Hydrocarbon oils used in industrial and other environments will gradually deteriorate over time due to oxidation of the hydrocarbons and contamination by other impurities.
  • the oxidation results in compounds such as acids, ketones, phenols and other oxygen containing molecules being formed in the oil.
  • Some of these molecules are strongly polar and will be oriented in an electrical field giving field losses when the oil is used as a transformer oil.
  • transformer oils may have been added/contaminated with halogenated organic compounds such as polychlorinated biphenyls (PCBs), the disposal or recycling of which possesses environmental hazards.
  • PCBs polychlorinated biphenyls
  • organo-copper and organo-iron compounds are known catalysts for catalytic oxidation of transformer oils. Hence, removal of these compounds from the used transformer oil will greatly improve the oxidation stability of the oil. Additionally, these organo-metallic compounds, mostly organo-copper compounds, could deteriorate the insulation properties of the insulation paper around the copper windings.
  • spots of copper oxide and/or copper sulphides can be formed on the insulation paper which will deteriorate the insulation properties of the insulating paper.
  • the copper oxide is being formed by interaction of organo-copper compounds with oxygen (or oxygenated compounds in the oil)
  • the copper sulphides are formed by interaction of organo-copper compounds with reactive organic sulphur compounds (OSC) present in the used old transformer oil.
  • OSC reactive organic sulphur compounds
  • the oil to be regenerated can either be collected and transported to the regeneration facilities or be regenerated on-site.
  • the former approach involves blending and logistical complications.
  • the on-site oil-reclamation approach is commonly carried out using adsorption methods, in which the used oxidised oil, e.g. a transformer oil, to be regenerated is passed over a solid adsorbent, which adsorbs the highly polar oxidised molecules.
  • the saturated solid adsorbent is itself regenerated by combustion at elevated temperatures.
  • a used oil containing oxygenated species can, however, also be regenerated chemically, in particular by the application of hydrotreatment technology. Hydrogenation effectively converts all the oxygenated organic molecules, both polar and non-polar oxygenated species, into less harmful compounds.
  • the hydrogenation technique also provides the opportunity to remove polychlorinated biphenyls (PCBs) and other halogenated compounds from the oil.
  • WO94/14731 discloses a process for simultaneous removal of halide from a halide containing organic compound and reduction of an oxygen containing compound in a hydrocarbon oil by exposing the oil to a catalyst in the presence of hydrogen and a hydrogen halide scavenger resulting in the reduction of the oxygen containing compound and the conversion of the halide to hydrohalic acid which is neutralized with the hydrogen halide scavenger.
  • the hydrogen halide i.e. the HCl is formed by hydrogenation of the PCBs in the used transformer oil. Hydrogen halides, besides being harmful substances can also cause metallurgical corrosion problems.
  • the hydrogen halide scavenger used in this prior art process is basically ammonia or any nitrogen-containing compound which upon reaction with hydrogen over a hydrotreament catalyst can form ammonia.
  • the role of the hydrogen halide scavenger is to react with hydrogen chloride, HCl, (which is the prime hydrogen halide in this connection) to form ammonium chloride (NH 4 Cl), hence "neutralising" the hydrochloric acid which can deactivate the catalyst. Since NH 4 Cl is a salt and can deposit/precipitate on the catalyst or heat exchangers resulting in corrosion under hydrogen media, etc., it was found necessary to keep the temperature of the reactor and the lines thereafter at a sufficiently high level to keep the majority of the NH 4 Cl in the gas phase.
  • ammonia is disadvantageous since the ammonium chloride formed thereby has to be removed. According to this prior art process this is done by contacting the effluents from the reactor with wash water to dissolve the ammonium chloride in a static mixer. The mixed stream from the static mixer is then passed to a high pressure separator where oil, water and gas phases containing NH 4 Cl, NH 3 and H 2 S is then sent to a neutraliser drum.
  • the hydrogen halide scavenger used in this prior art process is ammonia (NH 3 ) or any nitrogen-containing compound which upon reaction with hydrogen over a hydrotreament catalyst (or thermal decomposition) can form ammonia (NH 3 ). Ammonia is very corrosive and can cause serious corrosion problems to the equipment.
  • OSC organic sulphur compounds
  • concentration of these OSC can vary from 5-5000 ppm w/w on sulphur basis.
  • H 2 S hydrogen sulphide
  • Another big source of H 2 S formed in the hydrotreatment reactor is from the decomposition of so called spiking agents added to the feed oil.
  • ammonia or other nitrogen containing compounds to the feed which over the catalyst can form ammonia will result in a) material corrosion b) formation of ammonium sulphide and ammonium chloride which could result in pipe clogging , c) slippage of NH 3 from the system could result in pollution of a harmful compound; and d) need for additional processes and equipment for removal of ammonium chloride and ammonium sulphide such as a static mixer for water wash and neutralizer drum (see page 4, lines 16-23).
  • this prior art process may be configured as a mobile transformer oil treatment unit for on-site re-treatment of oils in transformers.
  • the oil of the transformer is transferred to a transportable storage tank which is also brought on-site. Oil is processed from this tank through the hydrogenation unit and the regenerated oils is transferred to a transportable product oil tank from which regenerated oil later will be returned to the transformer via a vacuum de-gassing unit.
  • insulating paper in the transformer which has adsorbed a considerable quantity of oil, may be damaged by its own weight.
  • the risks for such insulation paper damage are more probable in older transformers.
  • the insulating paper in the transformer may have very high contents of water which may have a negative impact on the performance of the transformer and the oil and water trapped in the insulation paper will retain impurities the removal of which is aimed at by means of the regeneration process thus causing contamination of the regenerated oil and faster oxidation thereof.
  • US-A-4 816 138 relates to a process for converting toxic liquid waste materials containing harmful amounts of biologically difficult to degrade organic halogen compounds into an innocuous hydrocarbon stream wherein the liquid feed is first filtered and then mixed with hydrogen and heated.
  • the warm mixture is passed over an adsorption column filled with alumina of high porosity in order to remove catalyst poisons contained in the feed. Then it is fed to a hydrogenolysis reactor.
  • the effluent from the reactor is cooled by being mixed with water; whereafter the mixture of water-effluent enters a separator. Oil + water go to an expansion tank.
  • the vapour phase is discharged by a gas line and the liquid phase is sent to a phase separation where water and hydrocarbon phase (product line 22) is discharged.
  • the claimed process is contemplated for the treatment of water-containing wastes as well as wastes which are substantially water-free but although transformer oil is mentioned as one example of a waste material to be treated, the claimed process is not particularly suited for transformer oil in view of the fact that the product of the process will have a high content water (water dissolved in hydrocarbon (oil)).
  • US-A-4 840 721 discloses a process for the regeneration of used transformer oil by catalytic hydrogenation at an elevated pressure and an elevated temperature, which process comprises: a) contacting said used oil with a first hot gaseous hydrogen stream in a first separator; contacting the bottom stream from the first separator with a second hot hydrogen stream in a second separator and separating a second hydrocarbonaceous vapour stream comprising hydrogen to remove sludge and insoluble in oil organo-metallic compounds, the preheating of the hydrogen-oil mixture is performed by contacting with hot hydrogen-rich gaseous; b) passing the second hydrocarbonaceaous vapor stream comprising hydrogen from step a) through a guard reactor in order to remove soluble in oil organo-metallic compounds, primarily organo-copper and organo-iron compounds and obtaining a hydrogen-oil mixture; c) subjecting the hydrogen-oil mixture from step b) to a catalytic hydrogenation in at least one hydrogenation fixed bed at a temperature within the range of from 100
  • no supplementary processes for the removal of ammonia and/or the un-reacted nitrogen-containing compounds are required.
  • no extra processes and equipment for the removal of the salts such as ammonium chloride and ammonium sulfide (which are formed upon the interaction of HCl or H 2 S with ammonia and/or N-containing compounds) is required.
  • a process for the regeneration of a used oil by catalytic hydrogenation at an elevated pressure and an elevated temperature wherein sludge and insoluble in oil organo-metallic compounds are removed by filtration and soluble in oil organo-metallic compounds, primarily organo-copper and organo-iron compounds are removed by means of a guard reactor before the used oil is subjected to hydrogenation, the effluent from the hydrogenation step is passed through an adsorbent bed to remove inorganic gases and then to a warm high pressure separator where the gas phase and the liquid hydrocarbon phases are separated. The latter is fed to a stripper unit from the bottom of which the regenerated oil is recovered.
  • used oil may be pumped from the bottom of the transformer via a buffer tank to the filters for the removal of sludge and insoluble in oil organo-metallic compounds and the regenerated oil is pumped back to the transformer while used oil is still remaining therein thus creating a back-mixing process.
  • Figure 1 is a diagrammatic representation of the process for the regeneration of a used oil according to the invention.
  • the flow pattern in Fig. 1 is presented as "up-flow” flow pattern.
  • the invented process is not limited to "up-flow” flow pattern but down flow pattern could also be applied.
  • a process for the regeneration of a used oil, in particular a used transformer oil, by catalytic hydrogenation at an elevated pressure and an elevated temperature comprises:
  • Water of the aqueous phase mentioned in step h) is partially water initially dissolved in the used oil, partially water formed as a by-product of catalytic hydrogenation of oxygenated compounds presented in the used oil.
  • filters 1 and 2 which can be operated alternating.
  • filters 1 and 2 are filter bags or plated filter cartridges rating from 1 to 100 microns, preferably from 1 to 50 microns.
  • FIG. 1 The flow pattern in Fig. 1 is schematically presented as up-flow mode (oil introduced from the bottom of the reactors 3, 4 and 5).
  • a down-flow mode (oil introduced from the top of the reactors 3, 4 and 5) is also in the scope of the present invention where the oil flows downwards through the reactors 3, 4 and 5. The rest of the process is the same with both down-flow and up-flow modes.
  • the combinations of up-flow and down-flow modes through the reactors 3, 4 and 5 is also covered by this invention.
  • the reaction mixture of oil and hydrogen thus obtained is heated up to a temperature within the range of from 100°C to 450°C, preferably from 200°C to 400°C and is then fed to catalytic guard reactors 3 and 4, operating alternatingly.
  • the guard reactor is operated at pressure within the range of 1 to 200 bars and preferably at 1 to 100 bars.
  • the reaction mixture is contacted with a catalyst with lower hydrotreatment activity, having wider pore size distribution.
  • Hydrogenation refers to the process of addition of hydrogen to the oil molecules to be refined.
  • Hydrogenation catalyst refers to substance which under operational condition by activation of hydrogen and the organic molecule could promote hydrogen addition reactions.
  • the conventional hydrotreatment catalyst in hydrogenation reactor (5) is usually comprised of one or more components of Group VIB metals of Table of Elements with one or more Group VIII non-noble metals of Table of Elements as promoters on a refractory support.
  • Hydrotreating catalyst generally contain Mo or W (or their combinations) as the group VI metal on alumina support promoted with cobalt, nickel, iron or combination thereof as the group VIII metal(s).
  • the amount of group VIII metal(s) component on the catalyst can vary from about 0.5 to 15 wt%; and the amount of group VIB metal(s) component can vary from 1 to 30 wt%.
  • the catalytic active metals are supported on low acidity porous support such as silica-alumina or alumina.
  • the metals on the catalyst are in sulphided state and during the hydrotreatment they should stay sulphided in order to exhibit their highest activity.
  • the catalyst can be: a) pre-sulphided, b) in-situ sulphided; or c) both a and b.
  • the active component of the catalyst should remain in sulphided state for highest activity.
  • the sulphide state of the active catalyst component in the course of hydrotreatment is maintained by: i) interaction of the catalyst active metals with H 2 S generated by hydrodesul-furization of sulphur-containing compound of the feed; and/or ii) by injection of a spiking agent to the feed.
  • any sulphur-containing compound, which upon hydrotreating conditions can undergo hydrogenation and decomposition to form hydrogen sulphide can be used.
  • Hydrotreating catalysts are commercially available, among others, catalysts from Tops ⁇ e, Albemarle; and Criterion could be used.
  • the catalyst in the guard reactor (3 and 4) is designated to trap and remove the metals from oil-soluble organo-metallic compounds such as organo-copper and organo-iron compounds in the feed used oil (de-metalation catalyst).
  • oil-soluble organo-metallic compounds such as organo-copper and organo-iron compounds in the feed used oil (de-metalation catalyst).
  • Such catalysts are similar to hydrogenation catalyst discussed earlier.
  • the active metals are supported on a large surface area support having wider pores and wider average pore size distribution, preferably having bimodal pore size distribution. It is widely known to the people familiar with the art of hydrotreatment and hydroprocessing that the guard reactor performance is maximized by grading the catalyst bed. The optimum bed grading is achieved by combination of e.g.
  • inert materials low or medium hydrogenation activity catalyst, variation in the carrier's surface area/pore size distribution and the catalyst shape along with catalyst particle sizes.
  • examples of commercially available hydrotreatment guard reactor catalysts are Ketjenfine KG 5, Ketjenfine KF 542, Ketjenfine KG 1, Ketjenfine KG 3 from and TK-711 and TK-551 from Tops ⁇ e.
  • the guard reactors 3 and 4 effectively remove organo-metallic species such as oil-soluble organo-copper and organo-iron compounds which may poison the hydrogenation catalyst from the oil to be regenerated. The presence of such organo-copper and organo-iron-compounds in the regenerated oil will deteriorate the performance of the transformer oil and the insulation properties of the transformer's copper windings insulation paper.
  • doping of the used oil to be regenerated may be performed by adding an organo-sulfur compound or organo-sulphur compounds (so-called spiking agent) before the oil is fed to guard reactors 3 and 4.
  • organo-sulfur compound or organo-sulphur compounds such as spiking agent
  • spiking agents may be any organo-sulphur compound which upon heating at a temperature >100°C over a hydrotreating catalyst can react with hydrogen or to decompose to produce H 2 S.
  • the aim of the spiking agent is to keep the catalyst in sulphide form.
  • the concentration of the spiking agent may vary between 10 and 1000 ppmw calculated on the feed oil.
  • the stream from guard reactors 3 and 4 is fed to a main hydrogenation fixed-bed reactor 5 in which the oil-hydrogen mixture is contacted with a highly active hydrogenation catalyst at temperatures within the range of from 100°C to 450°C and at pressures within the range from 1 bar to 200 bars, preferably at a temperature of 200-400°C and a pressure of 1-100 bars.
  • More than one reactor 5 can be applied in series, containing single bed or staged graded catalyst bed. Catalysts used are as aforementioned.
  • the undesired oxygen-containing molecules in the oil are catalytically converted in reactor 5 to desired ones by the catalytically addition of hydrogen to their structure.
  • the undesired reactive organo-sulphur containing compounds in the oil are also catalytically converted in reactor 5 to desired ones by the catalytically addition of hydrogen to their structure (hence the regenerated oil will have less or non corrosivity tendency toward the metal surfaces in the transformer).
  • Hydrogenation, hydrodesulphurization, hydrodeoxy-genation and, if required, hydrodechlorination reactions are carried out simultaneously over the hydrogenation catalyst in reactor 5.
  • the residence time of the oil in reactor 5, in terms of Liquid Hourly Space Velocity, LHSV, could be in the range of 0.1 to 15 h -1 ; and preferably in the range of 2 to 8 h -1 .
  • the preferred hydrogen-to-oil ratio (at STP) is in the range of 10 to 300 on volume basis and more preferably in the range of 10 to 100 (at STP).
  • the effluent from reactor 5 is passed through an adsorbent bed 6 or 7 in order to remove inorganic gases, i.e. H 2 S and possibly HCl, formed by the hydrogenation step in reactor 5 in which the H 2 S is formed by hydrogenation of the reactive organic sulphur compounds in the used transformer oil whereas the HCl is formed by the hydrogenation of chlorine containing molecules such as PCBs in the feed used transformer oil (i.e. if the feed contain PCBs).
  • the hydrogen chloride gas formed in reactor 5 can be adsorbed in adsorbent beds 6 or 7.
  • the adsorbent of adsorbent beds 6 or 7 for the adsorption of hydrogen chloride gas part thereof may be used for adsorption of hydrogen sulphide gas.
  • Adsorbent materials for use in adsorbent beds 6 and 7 are primarily based on alkaline and alkaline earth compounds which are commercially available, such as those which are discussed later in the text in connection with sorbent beds 12 and 13.
  • adsorbent bed 6 and/or 7 After having passed an adsorbent bed 6 and/or 7 the stream thus purified from inorganic gases, mainly hydrogen sulphide and hydrogen chloride, is fed to a warm high pressure separator 8 where it is separated into a gas phase and a liquid hydrocarbon phase. Separator 8 is operated at a temperature within the range of from 40 to 200 °C and at a pressure within the range from 1 to 200 bars, preferably at from 50 to 150°C and from 1 to 100 bars.
  • the liquid hydrocarbon phase leaving the warm high pressure separator 8 is subjected to a stripping process in a stripper unit 10 which may be operated at atmospheric or sub-atmospheric pressures, i.e. under pressures within the range of 1-760 mmHg and a temperature within the range of 10-200°C.
  • a stripper unit 10 which may be operated at atmospheric or sub-atmospheric pressures, i.e. under pressures within the range of 1-760 mmHg and a temperature within the range of 10-200°C.
  • nitrogen gas is used for the stripping process.
  • Regenerated oil is recovered from the condenser bottom of the stripper unit 10 (Line 1), whereas the gas phase is fed to a cold separator 11 to be separated into one mostly hydrocarbon phase, one mostly aqueous phase (i.e. two liquid phases; and a gas phase).
  • the liquid phases from cold separator 11 are sent to disposal (Lines 2, 3).
  • said process also comprises a first additional step, wherein the gas phase leaving the warm high pressure separator 8 is separated into a gas phase, a liquid hydrocarbon phase and an aqueous phase in a cold high pressure separator 9, and a second additional step wherein the liquid hydrocarbon phase from the cold high pressure separator 9 is fed into the stripper unit 10 while the aqueous phase is sent to disposal (Line 3).
  • Cold high pressure separator 9 may be operated at pressures within the range of from 1 to 200 bars and at temperatures within the range of from 30 to 100°C.
  • the separator 11 may be operated at atmospheric or sub-atmospheric pressures, preferably within the range of from 1 to 760 mmHg and at temperatures of 25°C to 120°C.
  • the gas phase from the respective cold separators 9 and 11 is preferably passed through sorption beds 13 and 12, respectively, in order to remove hydrogen sulphide and potentially hydrogen chloride gases.
  • the gas phases from separators 9 and 11 may be mixed and passed through a common sorption bed.
  • adsorbent beds 6 and 7 are omitted and thus the effluent from the hydrogenation fixed-bed 5 is fed directly into the warm high pressure separator 8.
  • the gas phase leaving warm high pressure separator 8 is subjected to a further separation in a cold high pressure separator 9 into two liquid phases and a gas phase whereas the liquid phase leaving warm high pressure separator 8 is fed to the stripper unit 10 as in the basic process illustrated in the drawing.
  • the gas phase obtained from the stripper unit 10 is subjected to a separation in a cold separator 11 into two liquid phases (one thereof being a mostly hydrocarbon phase and the other being a mostly aqueous phase) and a gas phase. Furthermore, like in case of the basic process, the gas phases from the cold high pressure separator 9 and cold separator 11, respectively, are passed through at least one sorbent bed 13 and 12, respectively, in order to remove at least one of mercaptanes and H 2 S therefrom.
  • the sorbent beds 12 and 13 can be filled with any inorganic compound or mixture of inorganic compounds that upon reaction with H 2 S and traces of HCl gases is able to form the corresponding stable metal sulphides and chlorides, respectively, and thereby removing said gases from the gas stream.
  • Materials suited for use in the sorbent beds 12 and 13 are commercially available and are based e.g.
  • iron oxides such as SulfatreatTM, Sulfur-RiteTM and Meida-G2TM
  • transition metal oxides such as ZnO and other mixed transition metal oxides doped with alkaline oxides deposited on alumina (e.g. PuraspecTM products); or activated carbon impregnated/deposited with alkali metal carbonate (such as Sofno-CarbTM).
  • the sorbent beds 12 and 13 are preferably packed with dual trap materials, one thereof being specifically adapted for the removal of HCl and the other for the removal of H 2 S.
  • the purified gas stream leaving sorbent beds 12 and 13 is passed through a catalytic combustor or a burner 14 where complete combustion of the flue gases to water and carbon dioxide is carried out or part or all of the purified gas stream is recycled through a gas compressor 15.
  • said gas phases are passed through a hydrogen purifier membrane in order to separate hydrogen gas from H 2 S, O 2 , N 2 and CO 2 .
  • the hydrogen lean stream from the hydrogen purifying membrane is fed to sorbent beds 12 and 13.
  • Hydrogen rich stream from the purifier membrane is fed to the gas compressor 15 to be recycled in the process whereas the hydrogen lean gases leaving sorbent beds 12 and 13 are sent to the catalytic combustor or burner 14. Part of the purified hydrogen may also be sent to burning by the burner 14.
  • the gas membrane to be used in this embodiment will be operated by a size exclusion approach.
  • Such membranes are commercially available, e.g. MedalTM from Air Liquide.
  • the process according to the invention is carried out in a mobile plant unit.
  • the mobile plant is placed on-site in the vicinity of a transformer and used transformer oil is pumped from the bottom of the transformer to a buffer tank before being subjected to the regeneration process according to the invention starting with step a) of said process and regenerated transformer oil from step g) of said process is returned into the transformer thus carrying out the process in a recirculation mode avoiding complete emptying of the transformer.
  • the regenerated oil when being pumped back into the transformer, will be contacted with non-regenerated oil therein (back-mixing) and become contaminated. For that reason the regeneration process should be continued until the volume of oil that has passed through the regeneration system is several times the volume of oil originally contained in the transformer, preferably at least three times that volume.
  • the volume of oil that has passed through the regeneration system is several times the volume of oil originally contained in the transformer, preferably at least three times that volume.
  • contaminated oil that is held by the insulating paper in the transformer and that would remain therein if completely emptying the transformer, will be brought into the circulation system and thus regenerated according to the present invention and there is no risk of causing damage to the insulating paper due to the own weight of said paper with oil adsorbed therein.
  • Such re-circulation will also help in removing the excess water in the transformer's insulating paper (in which some organic acid might be dissolved) and shift the paper water-oil equilibrium.
  • the used transformer oil is subjected to a treatment step before starting the regeneration process according to this embodiment.
  • the used transformer oil after being filtered for removal of coarse materials in filters (1 or 2), is fed to the stripper (10). This is done for dewatering (dehydration) of the transformer oil.
  • the stripper (10) is in this case operated at temperatures of 10-150°C and pressures of 1-760 mm Hg. The dehydrated oil is returned to the transformer and the removed water is collected from Line 3.
  • the used oil from the transformer is discharged to a separated dedicated tank called the feed tank.
  • the used transformer oil is further pumped from the aforementioned feed tank to the mobile regeneration unit for being regenerated.
  • the regenerated oil from the regeneration unit is fed to a receiver tank for the regenerated transformer oil with restored oil's electrical properties and will contain no or negligible amounts of oil-soluble organo-copper and organo-iron compounds.
  • Example 2 Similarly to Example 1 the required TAN and electrical properties are restored to the values required for good transformer oil.
  • Highly oxidised transformer oils were subjected to regeneration at conditions typical of examples one and two.
  • the copper content of the feed used oils (I-III) and their corresponding regenerated oils (I-III) were determined by atomic absorption spectrophotometry with graphite oven.
  • Table 3 the invented process completely removed the soluble in oil organo-copper compounds. Up to 80% of the soluble in oil organo-iron compounds were also removed. All the non-treated used oil samples failed the CCD test.
  • the regeneration of these oils resulted in an oil which passed the state of the art CCD test, indicating that the corrosive organic sulphur compounds in oil are removed by the process described in this invention.
  • Table 3 The properties of the feed used oils (I-III) and their corresponding regenerated oil (I-III).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (15)

  1. Verfahren zur Regenerierung von benutztem Transformatoröl durch katalytische Hydrierung bei einem erhöhten Druck und einer erhöhten Temperatur, wobei das Verfahren aufweist:
    a) Filtern des benutzten Öls, um schlammige und in Öl unlösliche metallorganischen Verbindungen in Filtern (1 und/oder 2) zu entfernen, woraufhin unter Druck gesetztes Wasserstoffgas zugesetzt wird und die auf diese Weise erhaltene Wasserstoff-Öl-Mischung einem Vorheizen unterzogen wird;
    b) Durchleiten der vorgeheizten Mischung von Schritt a) durch einen Schutzreaktor (3, 4), um in Öl lösliche metallorganische Verbindungen, in erster Linie kupferorganische und eisenorganische Verbindungen, zu entfernen;
    c) Unterziehen der Wasserstoff-Öl-Mischung von Schritt b) einer katalytischen Hydrierung in wenigstens einem Hydrierungsfestbett (5) bei einer Temperatur im Bereich von 100°C bis 450°C und bei einem erhöhten Druck;
    d) Durchleiten des Abflusses von Schritt c) durch ein Adsorptionsbett (6, 7), um in Schritt c) gebildete anorganische Gase zu entfernen;
    e) Abscheiden des Stroms aus Schritt d) in einem warmen Hochdruckabscheider (8) in eine Gasphase und eine flüssige Kohlenwasserstoffphase;
    f) Aussetzen der flüssigen Kohlenwasserstoffphase von dem warmen Hochdruckabscheider (8) einem Strippverfahren in einer Strippereinheit (10); und
    g) Rückgewinnen des regenerierten Öls von dem Boden der Strippereinheit (10),
    wobei das Verfahren in einer Rezirkulationsbetriebsart durch Pumpen von Transformatoröl von dem Boden des Transformators zu einem Puffertank vor dem Schritt a) und Rückführen von regeneriertem Transformatoröl von dem Schritt g) in den Transformator ausgeführt wird, ohne den Transformator vollständig zu leeren.
  2. Verfahren nach Anspruch 1, das zusätzlich aufweist:
    h) Abscheiden der Gasphase von dem in Schritt e) verwendeten warmen Hochdruckabscheider (8) in eine Gasphase und flüssige Kohlenwasserstoffphasen in einem kalten Hochdruckabscheider (9);
    i) Zuführen der flüssigen Kohlenwasserstoffphase von Schritt h) in die Strippereinheit (10) und der wässrigen Phase zur Entsorgung (Leitung 3).
  3. Verfahren nach Anspruch 1 oder 2, wobei der Schutzreaktor (3 oder 4) in Schritt b) bei einer Temperatur im Bereich von 100°C bis 450°C und bei einem erhöhten Druck von 1 bis 100 Bar über einem Hydrotreating-Katalysator betrieben wird.
  4. Verfahren nach Anspruch 1, wobei die Gasphase von der in Schritt f) verwendeten Strippereinheit (10) an einen kalten Abscheider (11) zugeführt wird, um in eine Gasphase und zwei flüssige Phasen abgeschieden zu werden, wobei die flüssigen Phasen von dem Abscheider (11) zur Entsorgung befördert werden (Leitungen 2 und 3).
  5. Verfahren nach Anspruch 2 und 3, wobei die Gasphase von dem kalten Hochdruckabscheider (9) und dem kalten Abscheider (11) durch Sorptionsbetten (12, 13) durchgeleitet wird, um Schwefelwasserstoff- und Chlorwasserstoffgase zu entfernen.
  6. Verfahren nach Anspruch 5, wobei die Gasphase von dem kalten Hochdruckabscheider (9) und dem kalten Abscheider (11) für die Wasserstoffgasreinigung durch ein Wasserstoffmembransystem, das vor den Sorptionsbetten (12, 13) angeordnet ist, geleitet wird.
  7. Verfahren nach Anspruch 1, wobei die katalytische Hydrierung von Schritt c) bei einem Druck im Bereich von 1 - 200 Bar, vorzugsweise 1 - 100 Bar, und/oder bei einer Temperatur im Bereich von 200 - 400°C ausgeführt wird.
  8. Verfahren nach einem der Ansprüche 1 - 7, wobei die katalytische Hydrierung von Schritt c) bei einer stündlichen Flüssigkeitsraumgeschwindigkeit (Liquid Hourly Space Velocity - LSVH) von 0,1 bis 15 h-1 ausgeführt wird.
  9. Verfahren nach einem der Ansprüche 1 - 8, wobei das Wasserstoff-Öl-Verhältnis der Zuführungsmischung von Schritt b) zu dem katalytischen Hydrierungsreaktor (5) auf Volumenbasis (bei STP) im Bereich von 5 bis 300 und vorzugsweise auf Volumenbasis (bei STP) in dem Bereich von 10 bis 100 liegt.
  10. Verfahren nach Anspruch 1, wobei wenigstens ein Teil, das aus der Gruppe ausgewählt wird, die aus Chlorwasserstoffgas und Schwefelwasserstoffgas besteht, von wenigstens einem der Adsorptionsbetten (6 und/oder 7) in Schritt d) adsorbiert wird.
  11. Verfahren nach einem der Ansprüche 1 - 10, wobei die Strippereinheit (10) bei Atmosphären- oder Unter-Atmosphärendruck und einer Temperatur im Bereich von 10 - 200°C, vorzugsweise bei einem Druck im Bereich von 1 bis 760 mm Hg betrieben wird.
  12. Verfahren nach einem der Ansprüche 1 - 11, wobei wenigstens ein Versetzungsmittel zu dem benutztem Öl zugesetzt wird, das vor dem Schutzreaktor (3, 4) erzeugt werden soll.
  13. Verfahren zur Regenerierung von benutztem Transformatoröl durch katalytische Hydrierung bei einem erhöhten Druck und einer erhöhten Temperatur, wobei das Verfahren aufweist:
    a) Filtern des benutzten Öls, um schlammige und in Öl unlösliche metallorganischen Verbindungen in Filtern (1 und/oder 2) zu entfernen, woraufhin unter Druck gesetztes Wasserstoffgas zugesetzt wird und die auf diese Weise erhaltene Wasserstoff-Öl-Mischung einem Vorheizen unterzogen wird;
    b) Durchleiten der vorgeheizten Mischung von Schritt a) durch einen Schutzreaktor (3, 4), um in Öl lösliche metallorganische Verbindungen, in erster Linie kupferorganische und eisenorganische Verbindungen, zu entfernen;
    c) Unterziehen der Wasserstoff-Öl-Mischung von Schritt b) einer katalytischen Hydrierung in wenigstens einem Hydrierungsfestbett (5) bei einer Temperatur im Bereich von 100°C bis 450°C und bei einem erhöhten Druck;
    e) Abscheiden des Stroms aus Schritt c) in einem warmen Hochdruckabscheider (8) in eine Gasphase und eine flüssige Kohlenwasserstoffphase;
    f) Aussetzen der flüssigen Kohlenwasserstoffphase von dem warmen Hochdruckabscheider (8) einem Strippverfahren in einer Strippereinheit (10); und
    g) Rückgewinnen des regenerierten Öls von dem Boden der Strippereinheit (10),
    wobei das Verfahren in einer Rezirkulationsbetriebsart durch Pumpen von Transformatoröl von dem Boden des Transformators zu einem Puffertank vor dem Schritt a) und Rückführen von regeneriertem Transformatoröl von dem Schritt g) in den Transformator ausgeführt wird, ohne den Transformator vollständig zu leeren, wobei
    - die Gasphase von Schritt e) einer weiteren Abscheidung in einem kalten Hochdruckabscheider (9) in zwei flüssige Phasen und eine Gasphase unterzogen wird;
    - die Gasphase, die von dem Strippverfahren von Schritt f) erhalten wird, einer Abscheidung in einem kalten Abscheider (11) in flüssige Phasen und eine Gasphase unterzogen wird;
    - die Gasphase von dem kalten Hochdruckabscheider (9) durch wenigstens ein Sorptionsbett (12, 13) hindurch geleitet wird, um HCl und/oder H2S daraus zu entfernen; und
    - die Gasphase von dem kalten Abscheider (11) durch wenigstens ein Sorptionsbett (12, 13) geleitet wird, um HCl und/oder H2S daraus zu entfernen.
  14. Verfahren nach einem der Ansprüche 1 - 13, das in einer mobilen Anlageneinheit ausgeführt wird.
  15. Verfahren nach einem der vorangehenden Ansprüche, wobei das verwendete Transformatoröl einer Vorbehandlung unterzogen wird, in welcher das verwendete Transformatoröl, nachdem es für die Entfernung grober Materialien in Filtern (1 oder 2) gefiltert wurde, zur Entwässerung an den Stripper (10) zugeführt wird und dann an den Transformator rückgeführt wird.
EP07748485.5A 2006-05-18 2007-05-10 Verfahren zur regenerierung von altöl Active EP2024038B1 (de)

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PCT/SE2007/050324 WO2007136340A1 (en) 2006-05-18 2007-05-10 Process for the regeneration of a used oil

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US20120141351A1 (en) * 2010-12-02 2012-06-07 General Electric Company Controlling the emission of volatile organic compounds from equipment for reclaiming oils
ES2694004T3 (es) 2014-03-17 2018-12-17 Hydrodec Development Corporation Pty Ltd Refinación de aceites usados
US9956553B2 (en) * 2016-06-28 2018-05-01 Chevron U.S.A. Inc. Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst
CN111298510B (zh) * 2020-03-31 2021-07-27 新疆金雪驰科技股份有限公司 一种润滑油过滤系统

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US4840721A (en) * 1988-03-16 1989-06-20 Uop Process for treating a temperature-sensitive hydrocarbonaceous stream containing a non-distillable component to produce a hydrogenated distillable hydrocarbonaceous product
NZ259290A (en) * 1992-12-23 1996-09-25 Commw Scient Ind Res Org Destruction/conversion of halide-containing organics (eg pcbs, ddt, etc) and solvent purification: use of hydrogen and catalyst to produce hydrogen halides for removal
US5354931A (en) * 1993-03-10 1994-10-11 Uop Process for hydrotreating an organic feedstock containing oxygen compounds and a halogen component
US5336834A (en) * 1993-05-20 1994-08-09 Uop Hydrocarbon conversion with additive loss prevention
US6461992B1 (en) * 1995-10-20 2002-10-08 Uop Llc Method for reducing chloride emissions from a moving bed catalyst regeneration process
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