EP0270813A1 - Process for reclaiming used oil - Google Patents

Process for reclaiming used oil Download PDF

Info

Publication number
EP0270813A1
EP0270813A1 EP87115860A EP87115860A EP0270813A1 EP 0270813 A1 EP0270813 A1 EP 0270813A1 EP 87115860 A EP87115860 A EP 87115860A EP 87115860 A EP87115860 A EP 87115860A EP 0270813 A1 EP0270813 A1 EP 0270813A1
Authority
EP
European Patent Office
Prior art keywords
oil
gas
waste oil
rich
hydrogen
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.)
Ceased
Application number
EP87115860A
Other languages
German (de)
French (fr)
Inventor
Johannes Dr. Albrecht
Rainer Dr. Reimert
Joachim Dr. Wilhelm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reimert Rainer Dr-Ing
Wilhelm Joachim Dr-Ing
Original Assignee
Reimert Rainer Dr-Ing
Wilhelm Joachim Dr-Ing
Metallgesellschaft AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Reimert Rainer Dr-Ing, Wilhelm Joachim Dr-Ing, Metallgesellschaft AG filed Critical Reimert Rainer Dr-Ing
Publication of EP0270813A1 publication Critical patent/EP0270813A1/en
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents

Definitions

  • the invention relates to a method for processing used oil.
  • This waste oil can e.g. are used motor oil, gear oil, lubricating oil, hydraulic oil, transformer oil or similar oils or mixtures of these oils.
  • Used oil contains various types of impurities that come from previous use, so used lubricating oil contains various additives and polychlorinated diphenyls (PCBs) that are highly toxic. If you want to recycle the used oil for reuse, you have to remove most of the contaminants and especially the halides, including PCB.
  • PCBs polychlorinated diphenyls
  • the object of the invention is to remove non-distillable impurities on the one hand and, on the other hand, halogen and heteroatom-containing components when working up waste oil.
  • the non-distillable impurities are primarily high-boiling aging products, additives and solids in waste oil, and the halogen-containing components in particular are PCBs.
  • the aim of the process is also to minimize the amount of waste to be disposed of.
  • this is achieved in that the waste oil is mixed with hydrogen-rich gas at a pressure of 50 to 250 bar, heated to a temperature of 350 to 500 ° C., solids are separated in a separation zone and removed as sludge, an evaporated, oil-rich phase withdrawing the separation zone and catalytically hydrogenating at temperatures from 300 to 400 ° C, the hydrogenated product is mixed with ammonia and degassed and separating an aqueous phase containing ammonium chloride from the degassed product.
  • the undesirable high-boiling components are separated from the waste oil by distillation in the separation zone.
  • the separation takes place under high pressure of 50 to 250 bar at temperatures of 350 to 500 ° C under hydrogenating conditions. This significantly improves the manageability of the residue.
  • the oil-rich vapor phase that forms in the separation zone is e.g. hydrogenated on a standard refinery catalyst based on cobalt-molybdenum or nickel-molybdenum. Chlorine compounds, including PCB, to HCl, oxygen compounds to H2O, nitrogen compounds to NH3 and sulfur compounds to H2S are largely converted. The hydrogenation takes place in the gas or trickle phase. The undesired components are washed out of the hydrogenated product by adding ammonia as ammonium compounds. Because ammonium chloride is formed from HCl, this neutralization reduces the corrosion problems.
  • the hydrogenation gases inevitably obtained in the hydrogenation e.g. CH4, ethane and propane can be used for underfire in the heater upstream of the separation zone.
  • a further development of the invention consists in degassing the hydrogenated product after addition of ammonia water in a first degassing stage at a pressure of 50 to 250 bar and temperatures of 20 to 60 ° C, withdrawing a hydrogen-containing gas and at least partially adding the waste oil, which oily phase to 1 to 5 bar relaxed and gives up a second degassing stage and from the second degassing stage at temperatures of 20 to 60 ° C a C1- to C4 hydrocarbons containing gas, an oil-rich product and an aqueous phase containing ammonium chloride is derived separately.
  • a sludge containing solids accumulates in the separation zone, which has to be disposed of but can also be worked up further, e.g. by filtering or centrifuging to recover valuable materials such as nickel and molybdenum.
  • a process water is formed which is contaminated with ammonium salts and water-soluble organic compounds and which is easy to clean biologically because there are no toxic chlorine compounds.
  • the waste oil to be processed comes from line (1) and is first freed of coarse solids in a mechanical filter (2).
  • the waste oil is compressed to 50 to 250 bar by a pump (3) and first reaches a heat exchanger (5) in line (4), in which the waste oil is first heated.
  • Hydrogen-rich gas from line (7) is mixed with the waste oil in line (6), whereupon the temperature of the mixture in the fired heater (10) is increased to 350 to 500 ° C.
  • the waste oil in the line (11) arrives at a separator (12) of a known type. In the bottom of the separator, the unevaporated portion of the waste oil collects in the form of a sludge, the solids, high molecular weight Contains impurities, aging products and additives. This sludge is removed from the process in line (13) and, if desired, can be sent for further processing.
  • An oil-rich vapor phase leaves the separator (12) through line (14), whereby hydrogen-rich gas is added to it from line (15). It makes sense to set the temperature of the mixture with this gas, which is passed in line (14) into the hydrogenation reactor (16).
  • the entry temperatures of the mixture into the reactor (16) are in the range from 300 to 400 ° C.
  • the hydrogenation of the mixture is preferably carried out in the gas phase or in the trickle phase over a hydrogenation catalyst which is known per se and is arranged in a fixed bed.
  • a cobalt-molybdenum or nickel-molybdenum catalyst is usually used as the hydrogenation catalyst.
  • the hydrogenated product leaves the reactor (16) in line (20), it now contains HCl, NH3, H2S, H2O and other hydrogenation products instead of the impurities in the mixture in line (14).
  • the product in the line (20) releases part of its sensible heat in the heat exchanger (5).
  • the hydrogenated product is added ammonia water from line (8), in such an amount that the HCl formed is neutralized.
  • the mixture flows through a cooler (22), which it leaves at temperatures of 20 to 60 ° C in the line (23).
  • a first separation of condensate and gas phase takes place in the separator (25) at a pressure which is only slightly below the pressure prevailing in the hydrogenation reactor (16).
  • the gas that is drawn off in line (26) mainly contains hydrogen.
  • the oil-rich condensate collecting in the separator (25) flows in the line (32) to an expansion valve (33) and is expanded there to a pressure of 1 to 5 bar.
  • gas and liquid are separated again. This creates a C1 to C4 hydrocarbons containing, combustible gas which is discharged in line (35) and also used as fuel in the heater (10) via line (31).
  • the product of the process, the oil-rich phase is drawn off from the separator (34) through line (36), and waste water is removed through line (37).
  • the wastewater contains ammonium compounds and, since it is not toxic, can be subjected to a biological treatment.
  • methanol is added to the waste oil through the dashed line (9), which is split into H2 and CO in the process. This produces the hydrogen-rich hydrogenation gas and dispenses with the supply of hydrogen through line (29).
  • the methanol is split in the heater (10) by thermal decomposition and also under the conditions prevailing in the separator (12) and in the hydrogenation reactor (16).
  • Used engine oil with a total chlorine content of 0.5% by weight is processed in a test facility on a laboratory scale.
  • 1.5 kg of the used oil are compressed to 140 bar per hour and mixed with 3.5 Nm3 / h of hydrogen-rich gas with an H2 content of 98%.
  • the mixture is heated to 445 ° C. and fed to the hot separator (12), in which a separation into a liquid phase and a gas phase takes place at a temperature of approximately 440 ° C.
  • the liquid phase obtained in the bottom of the separator on average 180 to 200 g / h, is a black, pasty, tar-like residue that contains the solids contained in the waste oil.
  • the gas phase is drawn off at the top of the hot separator (12) and cooled to 380 ° C. At this temperature, it is fed to the hydrogenation reactor (16), which contains 1.2 kg of a cobalt-molybdenum refinery catalyst as a fixed bed.
  • the commercially available catalyst consists of extrusions with a diameter of 3 mm.
  • the product flows through the catalyst bed from top to bottom, the temperature rising from 380 ° C to 384 ° C. 300 g of a 2% strength ammonia water is added to the hydrogenated product by means of a metering pump.
  • the mixture is cooled to room temperature in a cooler and expanded to normal pressure.
  • the liquid product consists of a practically chlorine-free, yellowish-clear oil phase, which is obtained on average in an amount of 1.3 kg / h.
  • an aqueous phase is formed, the amount of which corresponds approximately to the amount of ammonia water added and which is about 5% by weight.
  • % Contains ammonium chloride.
  • Example 1 The system of Example 1 is fed a mixture of used motor oil and methanol with a methanol content of 5% by weight in an amount of 1.5 kg / h.
  • the total chlorine content of the mixture is 0.5% by weight.
  • the mixture is compressed to 240 bar and mixed per hour with 800 Nl of hydrogen-containing gas that is generated in the process.
  • the gas is a mixture of H2 and CO with 33 vol.% CO.
  • the further treatment of the mixture is carried out as in Example 1.
  • As products an average of 1.2 kg of a largely chlorine-free oil and 980 Nl of gas per hour, which essentially consists of H2 and CO in a ratio of 2: 1 and a proportion of C1 - Contains up to C4 hydrocarbons of about 1 to 2 vol.%.
  • the hot separator (12) produces 200 g of a pasty residue per hour, which is flowable at temperatures of at least 250 ° C. Methanol is not detected in the products, which means that it is completely split into CO and H2 in the process.

Abstract

The used oil in line (1) is treated at a pressure of 50 to 250 bar with hydrogen-rich gas (7) and heated to a temperature of 350 to 500 DEG C. In a separation zone (12), solids (13) are separated off and removed as sludge, and a vapourised, oil-rich phase (14) is taken off from the separation zone. The oil-rich phase is catalytically hydrogenated in zone (16) at temperatures from 300 to 400 DEG C. The hydrogenated product is treated with ammonia (8) and degassed, and an aqueous phase (37) containing ammonium chloride is separated from the degassed product.

Description

Die Erfindung betrifft ein Verfahren zum Aufarbeiten von Altöl. Bei diesem Altöl kann es sich z.B. um gebrauchtes Motorenöl, Getriebeöl, Schmieröl, Hydrauliköl, Transformatorenöl oder ähnliche Öle oder Mischungen dieser Öle handeln.The invention relates to a method for processing used oil. This waste oil can e.g. are used motor oil, gear oil, lubricating oil, hydraulic oil, transformer oil or similar oils or mixtures of these oils.

Altöl enthält verschiedenartige Verunreinigungen, die aus der vorausgegangenen Nutzung stammen, so enthält gebrauchtes Schmieröl diverse Additive und polychlorierte Diphenyle (PCB), die hochgiftig sind. Wenn man das Altöl zur Wiederverwendung aufarbeiten will, muß man die Verunreinigungen und insbesondere die Halogenide, darunter PCB, weitgehend entfernen.Used oil contains various types of impurities that come from previous use, so used lubricating oil contains various additives and polychlorinated diphenyls (PCBs) that are highly toxic. If you want to recycle the used oil for reuse, you have to remove most of the contaminants and especially the halides, including PCB.

Der Erfindung liegt die Aufgabe zugrunde, bei der Aufarbeitung von Altöl einerseits nicht destillierbare Verunreinigungen und andererseits auch halogen- und heteroatomhaltige Komponenten zu entfernen. Bei den nicht destillierbaren Verunreinigungen handelt es sich vor allem um hochsiedende Alterungsprodukte, Additive und Feststoffe im Altöl und bei den halogenhaltigen Komponenten insbesondere um PCB. Ziel des Verfahrens ist es auch, die zu entsorgenden Abfallmengen zu minimieren. Erfindungsgemäß wird dies dadurch erreicht, daß man das Altöl bei einem Druck von 50 bis 250 bar mit wasserstoffreichem Gas versetzt, auf eine Temperatur von 350 bis 500°C erhitzt, in einer Abscheidezone Feststoffe abtrennt und als Schlamm entfernt, eine verdampfte, ölreiche Phase aus der Abscheidezone abzieht und bei Temperaturen von 300 bis 400°C katalytisch hydriert, das hydrierte Produkt mit Ammoniak versetzt und entgast und aus dem entgasten Produkt eine Ammoniumchlorid enthaltende wäßrige Phase abtrennt.The object of the invention is to remove non-distillable impurities on the one hand and, on the other hand, halogen and heteroatom-containing components when working up waste oil. The non-distillable impurities are primarily high-boiling aging products, additives and solids in waste oil, and the halogen-containing components in particular are PCBs. The aim of the process is also to minimize the amount of waste to be disposed of. According to the invention, this is achieved in that the waste oil is mixed with hydrogen-rich gas at a pressure of 50 to 250 bar, heated to a temperature of 350 to 500 ° C., solids are separated in a separation zone and removed as sludge, an evaporated, oil-rich phase withdrawing the separation zone and catalytically hydrogenating at temperatures from 300 to 400 ° C, the hydrogenated product is mixed with ammonia and degassed and separating an aqueous phase containing ammonium chloride from the degassed product.

Bei diesem Verfahren werden die unerwünschten hochsiedenden Komponenten in der Abscheidezone destillativ aus dem Altöl abgetrennt. Die Abscheidung erfolgt unter hohem Druck von 50 bis 250 bar bei Temperaturen von 350 bis 500°C unter hydrierenden Bedingungen. Die Handhabbarkeit des Rückstandes wird dadurch erheblich verbessert.In this process, the undesirable high-boiling components are separated from the waste oil by distillation in the separation zone. The separation takes place under high pressure of 50 to 250 bar at temperatures of 350 to 500 ° C under hydrogenating conditions. This significantly improves the manageability of the residue.

Die in der Abscheidezone entstehende ölreiche Dampfphase wird in der anschließenden katalytischen Hydrierung z.B. an einem Standard-Raffineriekatalysator auf der Basis Kobalt-Molybdän oder Nickel-Molybdän hydriert. Dabei werden Chlorverbindungen, auch PCB, zu HCl, Sauerstoff-Verbindungen zu H₂O, Stickstoff-Verbindungen zu NH₃ und Schwefel-Verbindungen zu H₂S weitgehend umgewandelt. Die Hydrierung erfolgt in der Gas- oder Rieselphase. Aus dem hydrierten Produkt werden die unerwünschten Komponenten durch Zusatz von Ammoniak als Ammoniumverbindungen ausgewaschen. Da dabei aus HCl Ammoniumchlorid entsteht, vermindert diese Neutralisierung die Korrosionsprobleme. Die bei der Hydrierung zwangsläufig anfallenden Hydriergase, z.B. CH₄, Äthan und Propan, können zur Unterfeuerung im Erhitzer, der der Abscheidezone vorgeschaltet ist, benutzt werden.The oil-rich vapor phase that forms in the separation zone is e.g. hydrogenated on a standard refinery catalyst based on cobalt-molybdenum or nickel-molybdenum. Chlorine compounds, including PCB, to HCl, oxygen compounds to H₂O, nitrogen compounds to NH₃ and sulfur compounds to H₂S are largely converted. The hydrogenation takes place in the gas or trickle phase. The undesired components are washed out of the hydrogenated product by adding ammonia as ammonium compounds. Because ammonium chloride is formed from HCl, this neutralization reduces the corrosion problems. The hydrogenation gases inevitably obtained in the hydrogenation, e.g. CH₄, ethane and propane can be used for underfire in the heater upstream of the separation zone.

Eine Weiterbildung der Erfindung besteht darin, daß man das hydrierte Produkt nach Zugabe von Ammoniakwasser in einer ersten Entgasungsstufe bei einem Druck von 50 bis 250 bar und Temperaturen von 20 bis 60°C entgast, ein wasserstoffhaltiges Gas abzieht und mindestens teilweise dem Altöl zugibt, die ölhaltige Phase auf 1 bis 5 bar entspannt und einer zweiten Entgasungsstufe aufgibt und aus der zweiten Entgasungsstufe bei Temperaturen von 20 bis 60°C ein C₁- bis C₄-Kohlenwasserstoffe enthaltendes Gas, ein ölreiches Produkt und eine Ammoniumchlorid enthaltende wäßrige Phase getrennt ableitet.A further development of the invention consists in degassing the hydrogenated product after addition of ammonia water in a first degassing stage at a pressure of 50 to 250 bar and temperatures of 20 to 60 ° C, withdrawing a hydrogen-containing gas and at least partially adding the waste oil, which oily phase to 1 to 5 bar relaxed and gives up a second degassing stage and from the second degassing stage at temperatures of 20 to 60 ° C a C₁- to C₄ hydrocarbons containing gas, an oil-rich product and an aqueous phase containing ammonium chloride is derived separately.

Beim Verfahren fällt in der Abscheidezone ein feststoffhaltiger Schlamm an, der zu entsorgen ist, aber auch noch weiter aufgearbeitet werden kann, z.B. durch Filtrieren oder Zentrifugieren, um Wertstoffe, etwa Nickel und Molybdän, wiederzugewinnen. Ferner entsteht ein mit Ammoniumsalzen und wasserlöslichen organischen Verbindungen verunreinigtes Prozeßwasser, das sich biologisch leicht reinigen läßt, weil toxische Chlor-Verbindungen fehlen.In the process, a sludge containing solids accumulates in the separation zone, which has to be disposed of but can also be worked up further, e.g. by filtering or centrifuging to recover valuable materials such as nickel and molybdenum. In addition, a process water is formed which is contaminated with ammonium salts and water-soluble organic compounds and which is easy to clean biologically because there are no toxic chlorine compounds.

Ausgestaltungen des Verfahrens werden mit Hilfe der Zeichnung erläutert.Embodiments of the method are explained with the aid of the drawing.

Das aufzuarbeitende Altöl kommt aus der Leitung (1) und wird zunächst in einem mechanischen Filter (2) von groben Feststoffen befreit. Durch eine Pumpe (3) wird das Altöl auf 50 bis 250 bar komprimiert und gelangt in der Leitung (4) zunächst zu einem Wärmeaustauscher (5), in welchem eine erste Erhitzung des Altöls erfolgt. Dem Altöl in der Leitung (6) wird wasserstoffreiches Gas aus der Leitung (7) zugemischt, worauf die Temperatur des Gemisches im gefeuerten Erhitzer (10) auf 350 bis 500°C erhöht wird. Mit diesen Temperaturen gelangt das Altöl in der Leitung (11) zu einem Abscheider (12) an sich bekannter Bauart. Im Sumpf des Abscheiders sammelt sich der unverdampfte Anteil des Altöls in Form eines Schlammes, der Feststoffe, hochmolekulare Verunreinigungen, Alterungsprodukte und Additive enthält. Dieser Schlamm wird in der Leitung (13) aus dem Verfahren entfernt und kann, falls gewünscht, einer weiteren Aufarbeitung zugeführt werden.The waste oil to be processed comes from line (1) and is first freed of coarse solids in a mechanical filter (2). The waste oil is compressed to 50 to 250 bar by a pump (3) and first reaches a heat exchanger (5) in line (4), in which the waste oil is first heated. Hydrogen-rich gas from line (7) is mixed with the waste oil in line (6), whereupon the temperature of the mixture in the fired heater (10) is increased to 350 to 500 ° C. With these temperatures, the waste oil in the line (11) arrives at a separator (12) of a known type. In the bottom of the separator, the unevaporated portion of the waste oil collects in the form of a sludge, the solids, high molecular weight Contains impurities, aging products and additives. This sludge is removed from the process in line (13) and, if desired, can be sent for further processing.

Eine ölreiche Dampfphase verläßt den Abscheider (12) durch die Leitung (14), wobei man ihr aus der Leitung (15) wasserstoffreiches Gas zumischt. Es bietet sich an, mit diesem Gas die Temperatur des Gemisches einzustellen, das man in der Leitung (14) in den Hydrierreaktor (16) leitet. Die Eintrittstemperaturen des Gemisches in den Reaktor (16) liegen im Bereich von 300 bis 400°C. Im Reaktor (16) erfolgt an einem an sich bekannten Hydrierkatalysator, der im Festbett angeordnet ist, die Hydrierung des Gemisches bevorzugt in der Gasphase oder auch in der Rieselphase. Als Hydrierkatalysator verwendet man üblicherweise einen Kobalt-Molybdän- oder Nickel-Molybdän-Katalysator.An oil-rich vapor phase leaves the separator (12) through line (14), whereby hydrogen-rich gas is added to it from line (15). It makes sense to set the temperature of the mixture with this gas, which is passed in line (14) into the hydrogenation reactor (16). The entry temperatures of the mixture into the reactor (16) are in the range from 300 to 400 ° C. In the reactor (16), the hydrogenation of the mixture is preferably carried out in the gas phase or in the trickle phase over a hydrogenation catalyst which is known per se and is arranged in a fixed bed. A cobalt-molybdenum or nickel-molybdenum catalyst is usually used as the hydrogenation catalyst.

Das hydrierte Produkt verläßt den Reaktor (16) in der Leitung (20), es enthält anstelle der Verunreinigungen des Gemisches in der Leitung (14) nunmehr HCl, NH₃, H₂S, H₂O und weitere Hydrierprodukte. Das Produkt in der Leitung (20) gibt einen Teil seiner fühlbaren Wärme im Wärmeaustauscher (5) ab. In der Leitung (21) gibt man dem hydrierten Produkt Ammoniakwasser aus der Leitung (8) zu, und zwar in einer solchen Menge, daß das entstandene HCl neutralisiert wird. Das Gemisch strömt durch einen Kühler (22), den es mit Temperaturen von 20 bis 60°C in der Leitung (23) verläßt. Im Abscheider (25) erfolgt bei einem Druck, der nur wenig unter dem im Hydrierreaktor (16) herrschenden Druck liegt, eine erste Trennung von Kondensat und Gasphase. Das Gas, das in der Leitung (26) abzieht, enthält vor allem Wasserstoff. Der größere Teil des Gases strömt in der Leitung (7) unter der Wirkung des Kompressors (28) zurück zur Altölaufarbeitung, wobei frischer Wasserstoff aus der Leitung (29) zugegeben wird. Ein Teil des von der Pumpe (28) geförderten wasserstoffhaltigen Gases wird in der Leitung (15) abgezweigt. Man kann einen Teil des Gases der Leitung (26) über das Entspannungsventil (30) leiten und in der Leitung (31) zum gefeuerten Erhitzer (10) führen, wo es als Brennstoff dient.The hydrogenated product leaves the reactor (16) in line (20), it now contains HCl, NH₃, H₂S, H₂O and other hydrogenation products instead of the impurities in the mixture in line (14). The product in the line (20) releases part of its sensible heat in the heat exchanger (5). In line (21), the hydrogenated product is added ammonia water from line (8), in such an amount that the HCl formed is neutralized. The mixture flows through a cooler (22), which it leaves at temperatures of 20 to 60 ° C in the line (23). A first separation of condensate and gas phase takes place in the separator (25) at a pressure which is only slightly below the pressure prevailing in the hydrogenation reactor (16). The gas that is drawn off in line (26) mainly contains hydrogen. The Major part of the gas flows in line (7) under the action of the compressor (28) back to the waste oil processing, fresh hydrogen being added from line (29). Part of the hydrogen-containing gas delivered by the pump (28) is branched off in the line (15). You can pass a portion of the gas in line (26) via the expansion valve (30) and lead in line (31) to the fired heater (10), where it serves as fuel.

Das sich im Abscheider (25) sammelnde ölreiche Kondensat strömt in der Leitung (32) zu einem Entspannungsventil (33) und wird dort auf einen Druck von 1 bis 5 bar entspannt. Im anschließenden Abscheider (34) wird erneut Gas und Flüssigkeit getrennt. Dabei entsteht ein C₁- bis C₄-Kohlenwasserstoffe enthaltendes, brennbares Gas, das man in der Leitung (35) abführt und über die Leitung (31) ebenfalls als Brennstoff im Erhitzer (10) benutzt. Das Produkt des Verfahrens, die ölreiche Phase, zieht man durch die Leitung (36) aus dem Abscheider (34) ab, Abwasser entfernt man durch die Leitung (37). Das Abwasser enthält Ammoniumverbindungen und kann, da es nicht toxisch ist, einer biologischen Reinigung unterzogen werden.The oil-rich condensate collecting in the separator (25) flows in the line (32) to an expansion valve (33) and is expanded there to a pressure of 1 to 5 bar. In the subsequent separator (34), gas and liquid are separated again. This creates a C₁ to C₄ hydrocarbons containing, combustible gas which is discharged in line (35) and also used as fuel in the heater (10) via line (31). The product of the process, the oil-rich phase, is drawn off from the separator (34) through line (36), and waste water is removed through line (37). The wastewater contains ammonium compounds and, since it is not toxic, can be subjected to a biological treatment.

Wo Wasserstoff nicht zur Verfügung steht, gibt man dem Altöl durch die gestrichelt eingezeichnete Leitung (9) Methanol zu, das im Verfahren zu H₂ und CO gespalten wird. Dadurch erzeugt man sich das wasserstoffreiche Hydriergas und verzichtet auf die Wasserstoffzufuhr durch die Leitung (29). Die Spaltung des Methanols erfolgt im Erhitzer (10) durch thermische Zersetzung und auch unter den Bedingungen, die im Abscheider (12) und im Hydrierreaktor (16) herrschen.Where hydrogen is not available, methanol is added to the waste oil through the dashed line (9), which is split into H₂ and CO in the process. This produces the hydrogen-rich hydrogenation gas and dispenses with the supply of hydrogen through line (29). The methanol is split in the heater (10) by thermal decomposition and also under the conditions prevailing in the separator (12) and in the hydrogenation reactor (16).

BEISPIEL 1EXAMPLE 1

In einer Versuchsanlage im Labormaßstab wird gebrauchtes Motorenöl mit einem Gesamtchlorgehalt von 0,5 Gew.% aufgearbeitet. Pro Stunde werden 1,5 kg des Altöls auf 140 bar komprimiert und mit 3,5 Nm³/h an wasserstoffreichem Gas mit einem H₂-Gehalt von 98 % vermischt. Die Mischung wird auf 445°C erhitzt und dem Heißabscheider (12) zugeleitet, in welchem bei einer Temperatur von etwa 440°C eine Auftrennung in eine Flüssigphase und eine Gasphase erfolgt. Die im Sumpf des Abscheiders anfallende Flüssigphase, im Mittel 180 bis 200 g/h, ist ein schwarzer, pastöser, teerähnlicher Rückstand, der die im Altöl enthaltenen Feststoffe enthält.Used engine oil with a total chlorine content of 0.5% by weight is processed in a test facility on a laboratory scale. 1.5 kg of the used oil are compressed to 140 bar per hour and mixed with 3.5 Nm³ / h of hydrogen-rich gas with an H₂ content of 98%. The mixture is heated to 445 ° C. and fed to the hot separator (12), in which a separation into a liquid phase and a gas phase takes place at a temperature of approximately 440 ° C. The liquid phase obtained in the bottom of the separator, on average 180 to 200 g / h, is a black, pasty, tar-like residue that contains the solids contained in the waste oil.

Die Gasphase wird am Kopf des Heißabscheiders (12) abgezogen und auf 380°C gekühlt. Mit dieser Temperatur wird sie dem Hydrierreaktor (16) aufgegeben, der 1,2 kg eines Kobalt-Molybdän-Raffineriekatalysators als Festbett enthält. Der handelsübliche Katalysator besteht aus Strangpreßlingen mit 3 mm Durchmesser. Das Produkt durchströmt das Katalysatorbett von oben nach unten, wobei die Temperatur von 380°C auf 384°C ansteigt. Dem hydrierten Produkt wird durch eine Dosierpumpe pro Stunde 300 g eines 2-%igen Ammoniakwassers zugegeben. In einem Kühler wird das Gemisch auf Raumtemperatur abgekühlt und auf Normaldruck entspannt. Dabei fällt ein wasserstoffreiches Gas an, das noch C₁- bis C₄-Kohlenwasserstoffe in einer Menge von 8,5 l/h enthält. Das Flüssigprodukt besteht aus einer praktisch chlorfreien, gelblich-klaren Ölphase, welche im Mittel in einer Menge von 1,3 kg/h erhalten wird, daneben entsteht eine wäßrige Phase, deren Menge etwa der zugegebenen Menge an Ammoniakwasser entspricht und die etwa 5 Gew.% Ammoniumchlorid enthält.The gas phase is drawn off at the top of the hot separator (12) and cooled to 380 ° C. At this temperature, it is fed to the hydrogenation reactor (16), which contains 1.2 kg of a cobalt-molybdenum refinery catalyst as a fixed bed. The commercially available catalyst consists of extrusions with a diameter of 3 mm. The product flows through the catalyst bed from top to bottom, the temperature rising from 380 ° C to 384 ° C. 300 g of a 2% strength ammonia water is added to the hydrogenated product by means of a metering pump. The mixture is cooled to room temperature in a cooler and expanded to normal pressure. This produces a hydrogen-rich gas that still contains C₁ to C₄ hydrocarbons in an amount of 8.5 l / h. The liquid product consists of a practically chlorine-free, yellowish-clear oil phase, which is obtained on average in an amount of 1.3 kg / h. In addition, an aqueous phase is formed, the amount of which corresponds approximately to the amount of ammonia water added and which is about 5% by weight. % Contains ammonium chloride.

BEISPIEL 2EXAMPLE 2

Der Anlage des Beispiels 1 wird eine Mischung aus gebrauchtem Motorenöl und Methanol mit einem Methanolgehalt von 5 Gew.% in einer Menge von 1,5 kg/h zugeführt. Der Gesamtchlorgehalt der Mischung beträgt 0,5 Gew.%. Die Mischung wird auf 240 bar komprimiert und pro Stunde mit 800 Nl wasserstoffhaltigem Gas, das im Verfahren erzeugt wird, vermischt. Das Gas ist eine Mischung aus H₂ und CO mit 33 Vol.% CO. Die weitere Behandlung der Mischung erfolgt wie im Beispiel 1. Als Produkte fallen im Mittel pro Stunde 1,2 kg eines weitgehend chlorfreien Öles und 980 Nl Gas an, das im wesentlichen aus H₂ und CO im Verhältnis 2:1 besteht und einen Anteil von C₁- bis C₄-Kohlenwasserstoffen von etwa 1 bis 2 Vol.% enthält. Der größte Teil des Gases wird der komprimierten Motorenöl-Methanol-Mischung zugegeben. Im Heißabscheider (12) fallen pro Stunde 200 g eines pastösen Rückstandes an, der bei Temperaturen von mindestens 250°C fließfähig ist. Methanol wird in den Produkten nicht nachgewiesen, was bedeutet, daß es im Prozeß vollständig zu CO und H₂ gespalten wird.The system of Example 1 is fed a mixture of used motor oil and methanol with a methanol content of 5% by weight in an amount of 1.5 kg / h. The total chlorine content of the mixture is 0.5% by weight. The mixture is compressed to 240 bar and mixed per hour with 800 Nl of hydrogen-containing gas that is generated in the process. The gas is a mixture of H₂ and CO with 33 vol.% CO. The further treatment of the mixture is carried out as in Example 1. As products, an average of 1.2 kg of a largely chlorine-free oil and 980 Nl of gas per hour, which essentially consists of H₂ and CO in a ratio of 2: 1 and a proportion of C₁ - Contains up to C₄ hydrocarbons of about 1 to 2 vol.%. Most of the gas is added to the compressed engine oil-methanol mixture. The hot separator (12) produces 200 g of a pasty residue per hour, which is flowable at temperatures of at least 250 ° C. Methanol is not detected in the products, which means that it is completely split into CO and H₂ in the process.

Claims (5)

1. Verfahren zum Aufarbeiten von Altöl, dadurch gekennzeichnet, daß man das Altöl bei einem Druck von 50 bis 250 bar mit wasserstoffreichem Gas versetzt, auf eine Temperatur von 350 bis 500°C erhitzt, in einer Abscheidezone Feststoffe abtrennt und als Schlamm entfernt, eine verdampfte, ölreiche Phase aus der Abscheidezone abzieht und bei Temperaturen von 300 bis 400°C katalytisch hydriert, das hydrierte Produkt mit Ammoniak versetzt und entgast und aus dem entgasten Produkt eine Ammoniumchlorid enthaltende wäßrige Phase abtrennt.1. A process for working up waste oil, characterized in that the waste oil is mixed with hydrogen-rich gas at a pressure of 50 to 250 bar, heated to a temperature of 350 to 500 ° C, separated in a separation zone and removed as sludge, a evaporated, oil-rich phase is withdrawn from the separation zone and catalytically hydrogenated at temperatures from 300 to 400 ° C., the hydrogenated product is mixed with ammonia and degassed, and an aqueous phase containing ammonium chloride is separated from the degassed product. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das hydrierte Produkt nach Zugabe von Ammoniak in einer ersten Entgasungsstufe bei einem Druck von 50 bis 250 bar und Temperaturen von 20 bis 60°C entgast, ein wasserstoffhaltiges Gas abzieht und mindestens teilweise dem Altöl zugibt, die ölhaltige Phase auf 1 bis 5 bar entspannt und einer zweiten Entgasungsstufe aufgibt und aus der zweiten Entgasungsstufe bei Temperaturen von 20 bis 60°C ein C₁- bis C₄-Kohlenwasserstoffe enthaltendes Gas, ein ölreiches Produkt und eine Ammoniumchlorid enthaltende wäßrige Phase getrennt ableitet.2. The method according to claim 1, characterized in that after the addition of ammonia in a first degassing step, the hydrogenated product is degassed at a pressure of 50 to 250 bar and temperatures of 20 to 60 ° C, a hydrogen-containing gas is drawn off and at least partially the waste oil admits, the oily phase relaxed to 1 to 5 bar and gives up a second degassing stage and from the second degassing stage at temperatures of 20 to 60 ° C a gas containing C₁ to C₄ hydrocarbons, an oil-rich product and an aqueous phase containing ammonium chloride are derived separately . 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man dem Altöl Methanol zugibt.3. The method according to claim 1 or 2, characterized in that methanol is added to the waste oil. 4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man das wasserstoffhaltige Gas aus der ersten Entgasungsstufe teilweise dem Altöl vor der Erhitzung und teilweise der verdampften ölreichen Phase vor der katalytischen Hydrierung zugibt.4. The method according to claim 2, characterized in that the hydrogen-containing gas from the first degassing stage is partly added to the waste oil before heating and partly to the evaporated oil-rich phase before the catalytic hydrogenation. 5. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man das C₁- bis C₄-Kohlenwasserstoffe enthaltende Gas aus der zweiten Entspannungsstufe als Brennstoff zum Erhitzen des Altöls verwendet.5. The method according to claim 2, characterized in that the gas containing C₁ to C₄ hydrocarbons from the second expansion stage is used as a fuel for heating the waste oil.
EP87115860A 1986-11-03 1987-10-29 Process for reclaiming used oil Ceased EP0270813A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3637255 1986-11-03
DE19863637255 DE3637255A1 (en) 1986-11-03 1986-11-03 METHOD FOR REFURBISHING ALTOEL

Publications (1)

Publication Number Publication Date
EP0270813A1 true EP0270813A1 (en) 1988-06-15

Family

ID=6312969

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87115860A Ceased EP0270813A1 (en) 1986-11-03 1987-10-29 Process for reclaiming used oil

Country Status (2)

Country Link
EP (1) EP0270813A1 (en)
DE (1) DE3637255A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299149A2 (en) * 1987-07-17 1989-01-18 Ruhrkohle Aktiengesellschaft Process for working up used lubricants by hydrogenation
EP0306164A1 (en) * 1987-08-13 1989-03-08 Uop Hydrogenating a temperature sensitive hydrocarbonaceous waste stream
CN115820333A (en) * 2021-09-17 2023-03-21 山东大学 Resource recycling method of waste lubricating oil sludge

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB856764A (en) * 1958-07-08 1960-12-21 British Petroleum Co Treatment of used diesel engine lubricating oil
EP0077564A2 (en) * 1981-10-19 1983-04-27 Phillips Petroleum Company De-ashing lubricating oils
US4387018A (en) * 1982-03-17 1983-06-07 The United States Of America As Represented By The United States Department Of Energy Method of removing polychlorinated biphenyl from oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB856764A (en) * 1958-07-08 1960-12-21 British Petroleum Co Treatment of used diesel engine lubricating oil
EP0077564A2 (en) * 1981-10-19 1983-04-27 Phillips Petroleum Company De-ashing lubricating oils
US4387018A (en) * 1982-03-17 1983-06-07 The United States Of America As Represented By The United States Department Of Energy Method of removing polychlorinated biphenyl from oil

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299149A2 (en) * 1987-07-17 1989-01-18 Ruhrkohle Aktiengesellschaft Process for working up used lubricants by hydrogenation
EP0299149A3 (en) * 1987-07-17 1989-03-08 Ruhrkohle Aktiengesellschaft Process for working up used lubricants by hydrogenation
EP0306164A1 (en) * 1987-08-13 1989-03-08 Uop Hydrogenating a temperature sensitive hydrocarbonaceous waste stream
AU613714B2 (en) * 1987-08-13 1991-08-08 Uop Treating a temperature-sensitive hydrocarbonaceous waste stream to produce a hydrogenated distillable and reusable hydrocarbonaceous product stream
CN115820333A (en) * 2021-09-17 2023-03-21 山东大学 Resource recycling method of waste lubricating oil sludge
CN115820333B (en) * 2021-09-17 2024-01-26 山东大学 Recycling recycling method of waste lubricating oil sludge

Also Published As

Publication number Publication date
DE3637255A1 (en) 1988-05-05

Similar Documents

Publication Publication Date Title
DE3623430C2 (en)
EP0287796B1 (en) Process for the hydroconversion of heavy and residual oils
DE2508713A1 (en) PROCESS FOR PROCESSING USED MINERAL OIL
DE1467198A1 (en) Process for purifying water containing NH3 and H2S
DE2654635B2 (en) Process for the continuous production of hydrocarbon oils from coal by cracking pressure hydrogenation
EP0073355A1 (en) Production of liquid hydrocarbons
DE2850540C2 (en) Process for processing waste oil
EP0503387A1 (en) Process for decomposition of aromatic nitro compounds contained in waste water
EP0372276B1 (en) Process for the recuperation of contaminated oils
DE3334509A1 (en) INTEGRATED METHOD FOR SOLVENT REFINING OF COAL
DE2940630C2 (en) Process for recycling used lubricating oils
DE10215679B4 (en) Direct thermochemical conversion of high molecular weight organic substances into low viscosity liquid fuels
EP0425893B1 (en) Process for the separation of a mixture of 1-methoxy-2-propanol and water into its components
DE3806365C1 (en)
EP0230543A1 (en) Process for recycling spent oil
EP0270813A1 (en) Process for reclaiming used oil
DE19516379A1 (en) Process for processing old or waste plastics
DE1493051A1 (en) Hydrogenation process
DE2711105C2 (en) Process for converting coal into hydrocarbons which are liquid under normal conditions
DE2259959C3 (en) Process for the production of heating oils by asphaltene separation and two-stage catalytic hydrogenative desulphurisation
DE3329222A1 (en) METHOD FOR COOLING LIQUID WITH AN ACTIVATED ZINC SULFIDE CATALYST
DE2718950C2 (en) Process for the attachment of hydrogen to coal
EP0209665A1 (en) Coal hydrogenation process by liquid phase and fixed-bed catalyst hydrogenation
DE3443977C2 (en)
EP1601437A1 (en) Method for preparing oil/water emulsions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT SE

17P Request for examination filed

Effective date: 19881208

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WILHELM, JOACHIM, DR.-ING.

Owner name: REIMERT, RAINER, DR.-ING.

17Q First examination report despatched

Effective date: 19890731

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19891215

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WILHELM, JOACHIM, DR.

Inventor name: REIMERT, RAINER, DR.

Inventor name: ALBRECHT, JOHANNES, DR.