EP0299149A2 - Process for working up used lubricants by hydrogenation - Google Patents

Process for working up used lubricants by hydrogenation Download PDF

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Publication number
EP0299149A2
EP0299149A2 EP88105856A EP88105856A EP0299149A2 EP 0299149 A2 EP0299149 A2 EP 0299149A2 EP 88105856 A EP88105856 A EP 88105856A EP 88105856 A EP88105856 A EP 88105856A EP 0299149 A2 EP0299149 A2 EP 0299149A2
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Prior art keywords
hydrogenation
products
oils
oil
waste
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EP88105856A
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German (de)
French (fr)
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EP0299149A3 (en
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Josef Dr. Langhoff
Alfons Dr. Jankowski
Harald Dr. Weber
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RAG AG
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Ruhrkohle AG
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/908—Organic
    • Y10S210/909—Aromatic compound, e.g. pcb, phenol

Definitions

  • the invention relates to a process for the hydrogenative processing of waste oils into secondary refinates in the form of lubricating oils with the addition of hydrogen.
  • waste oils are currently generated annually, which is about 50% of the fresh oil used in the same period.
  • a large part of the waste oil is processed into so-called secondary refinements.
  • the processing of waste oil into secondary refinements requires that the waste oil is contaminated only to a very small extent with components that lead to environmental damage when the secondary refinate is used.
  • Organochlorine compounds, in particular PCB polychlorinated biphenyls
  • PCB polychlorinated biphenyls
  • the highly toxic chlorinated dibenzodioxins and dibenzofurans can arise if the second raffinate, e.g. B. burns as lubricating oil in internal combustion engines at low temperature.
  • Polychlorinated biphenyls are e.g. B. in cutting oils, hydraulic oils, especially for mining, transformer oils and. ⁇ . included, because this makes the oils incombustible.
  • the PCB is non-biodegradable, persistent and ubiquitous; it has a structure similar to DDT (dichlorodiphenyltrichloroethane) and is also increasingly found in the food chain, such as in fish, in breast milk and the like.
  • Waste oils contaminated in this or a similar way which contain more than 20 mg / kg PCB and / or more than 0.5% by weight organochlorine compounds, are considered waste and are therefore subject to the regulations on waste disposal. The maximum limits will go even further in the future be lowered.
  • Waste oils with contamination above these values must be disposed of as hazardous waste in an approved hazardous waste disposal facility, e.g. B. a high temperature incinerator. Their capacity in the Federal Republic of Germany is completely inadequate, so that there are already bottlenecks in disposal. In high-temperature combustion, the waste oil is burned at temperatures above 1,200 ° C and residence times of more than 0.3 seconds, which prevents the formation of poisons such as dioxin.
  • the physical treatment consists of a multi-stage cleaning process in which water and highly volatile components are first separated from the waste oil under atmospheric pressure and at 150 ° C. A gas oil fraction is then separated off in a second stage at a vacuum of 20 mbar and 270 ° C. This is followed by a third stage, a high-vacuum short-path distillation, which takes place in a special thin-film evaporator at 310 ° C and a vacuum of 2 mbar using indirect heat transfer with simultaneous high turbulence in the heat transfer zones.
  • the fourth stage is followed by hydrofinishing, in which only such impurities are contained in the purified oil fraction that have the same boiling range as the purified oil fraction itself - they are mainly components containing chlorine, oxygen and nitrogen.
  • the hydrofinishing takes place at pressures of about 50 bar and temperatures between 300 and 350 ° C, the impurities being separated off as ammonium chloride, gas oil and water and any sulfur impurities present being removed as H2S.
  • organochlorine compounds or ethylene glycols from anti-freeze
  • the object of the invention is to obtain a process for the hydrogenative treatment of waste oils to give secondary refinates, in particular in the form of lubricating oils, while avoiding ecologically undesirable by-products or wastes, with which it is possible in particular to also treat waste oils which previously, especially due to their content of organochlorine compounds and in particular the PCB, could only be disposed of by special waste disposal plants.
  • This object is achieved according to the invention by a process of the type mentioned at the outset, in which the waste oil is first freed of coarse solids and subsequently hydrogenated in a sump phase at pressures of 30 to 300, preferably 150 bar and temperatures of 200 to 450, preferably 350 ° C. , is subjected and then a separation of the reaction products into the lubricating oil and by-products takes place.
  • the products produced by the invention by means of hydrogenating dechlorination can be reused as economically useful reuse.
  • the typical product properties of the lubricating oils are retained;
  • the process can also be used for the hydrogenative work-up of uncontaminated oils without producing ecologically harmful or questionable, that is to say ecologically undesirable, by-products or wastes, as are known from the sulfuric acid bleaching earth process;
  • So-called aging products of the oil as well as additives can be removed from the waste oil after the hydrogenation step in the sump phase without any problems;
  • the separation into residues and product oil is at the same time usability of relatively inexpensive catalysts less expensive than by known methods, eg. B. the CTI procedure.
  • waste oils for the purposes of the invention, “waste oils”, “secondary refinates”, “removal of coarse solids” and “hydrogenation in the bottom phase” mean the following:
  • Waste oils in the sense of this invention are oils which, due to their condition due to previous use, can no longer be used as intended.
  • Halogen-containing impurities can also be contained in the oil.
  • Secondary refinates are products that can be reused as lubricating oils after the method according to the invention has been applied and after the addition of conventional additives.
  • the waste oil is in the liquid state in the reaction space.
  • the hydrogenation takes place in the bottom phase, preferably in the presence of a weakly hydrogenation-active catalyst.
  • a weakly hydrogenation-active catalyst include, in particular, Fe catalysts, such as Bavarian mass (red mud) or support materials impregnated with iron salts.
  • the hydrogenation takes place in the bottom phase with the addition of a neutralizing agent, in particular a Na salt of a weak acid, such as sodium sulfide, more contaminated waste oils, ie those with a relatively high content of organochlorine compounds, can also be used as secondary raffinates
  • a neutralizing agent in particular a Na salt of a weak acid, such as sodium sulfide
  • a weak acid such as sodium sulfide
  • more contaminated waste oils ie those with a relatively high content of organochlorine compounds
  • the neutralizing agent is preferably added before the hydrogen is added, in particular together with a catalyst. Typical The amounts added are between one and three times the stoichiometric amount, based on chlorine in the used oil.
  • the separation of the reaction products of the hydrogenation in the bottom phase into the lubricating oil or a preliminary product of the lubricating oil on the one hand and in by-products on the other hand takes place in a hot separator in which a top product containing the gases is separated from a bottom product containing all liquids and solids.
  • a hot cutter is usually operated at about 30 to 50 ° C below the temperature in the bottom phase reactor.
  • the bottom product of the hot separator is preferably distilled in a vacuum column.
  • the resulting vacuum residue contains, as solids, in particular the catalyst and sodium chloride, which has formed from the dechlorination of organochlorine compounds.
  • the top products of the vacuum column and the hot separator are preferably combined to obtain the lubricating oil.
  • a hydrogenation in the gas phase following the separation step of the solid reaction products from the hydrogenation in the bottom phase from the liquid reaction products leads to an improvement in the quality of the secondary raffinate to be obtained in the form of lubricating oils.
  • “hydrogenation in the gas phase” is understood to mean hydrogenation of the liquid or vaporous oils over a refining catalyst.
  • Nickel / molybdenum or cobalt / molybdenum catalysts are preferred as refining catalysts
  • the coarse solids in particular by filtration, used oil with an organochlorine content of 0.6 wt .-% is used together with 3 wt .-% Bavarian mass as a catalyst and 2.7% Na2S (2-fold stoichiometric amount) as a neutralizing agent.
  • the mixture to be hydrogenated is heated to 350 ° C. in a preheater 1 at 150 bar before being fed into the bottom phase reactor 2 and then hydrogenated in the bottom phase reactor 2 at 150 bar and 350 ° C.
  • reaction products from the hydrogenation in the bottom phase are separated in a hot separator 3, the vaporous products being taken off overhead, the liquid phase and the solids as bottom product at the lower end of the hot separator 3.
  • the bottom product withdrawn from the hot separator 3 is separated in a vacuum distillation column 4 at temperatures of 350 ° C. and pressures of 20 mbar into a liquid top product and into a vacuum residue which is still pumpable and contains the solids if possible.
  • the organochlorine compounds split off as chlorine in the bottom phase in the hydrogenation and bound as sodium chloride, as well as additives and aging products contained in the waste oil, are separated off.
  • the top products from the hot separator 3 and the vacuum distillation column 4 are subsequently hydrogenated in a gas phase reactor 5 under the following working conditions: Pressure 100 bar Temperature 350 ° C As a catalyst, a nickel / molybdenum catalyst is used on - Al2O3.
  • reaction product of the hydrogenation is separated into liquid and gaseous components at temperatures of approximately 300 ° C. and pressures of 100 bar.
  • the resulting gas preferably hydrogen, is recycled after gas cleaning.
  • the liquid phase is relaxed and the product oil is drawn off.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
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Abstract

Spent oils are processed by hydrogenation to give second raffinates in the form of lubricating oils. Ecologically undesired by-products or wastes are avoided in this process, without expensive separation steps or reaction conditions or the use of expensive catalysts being necessary. In particular, the result is that even highly contaminated spent oils, i.e. those which contain organochlorine compounds, especially PCB, chlorinated dioxines and dibenzofurans in concentrations above defined limits, can also be re-utilised as a second raffinate, especially as a lubricating oil; therefore, they no longer have to be destroyed, for example in a high-temperature combustion process. For this purpose, the spent oil is first freed only of coarse solids and then subjected, with addition of hydrogen, to hydrogenation in a liquid phase at pressures of preferably 150 bar and temperatures of preferably 350 DEG C; the reaction products are then separated into the lubricating oil and, in particular, solids- containing by-products.

Description

Die Erfindung betrifft ein Verfahren zur hydrierenden Aufarbei­tung von Altölen zu Zweitraffinaten in Form von Schmierölen unter Zugabe von Wasserstoff.The invention relates to a process for the hydrogenative processing of waste oils into secondary refinates in the form of lubricating oils with the addition of hydrogen.

Allein in der Bundesrepublik Deutschland fallen derzeit jähr­lich etwa 500 000 t Altöle an, das sind etwa 50 % des im selben Zeitraum eingesetzten Frischöles. Ein Großteil des Altöles wird zu sogenannten Zweitraffinaten aufbereitet. Die Aufbereitung von Altöl zu Zweitraffinaten setzt aber voraus, daß das Altöl nur in äußerst geringem Umfang mit solchen Komponenten kontami­niert ist, die bei der Weiterverwendung des Zweitraffinates zu Umweltschäden führen. Besonders störend sind Organochlorver­bindungen, insbesondere das PCB (polychlorierte Biphenyle); aus diesen Verunreinigungen können nämlich die hochgiftigen chlorierten Dibenzodioxine und Dibenzofurane entstehen, wenn das Zweitraffinat, z. B. als Schmieröl in Brennkraftmaschinen bei niedriger Temperatur verbrennt. Polychlorierte Biphenyle sind z. B. in Schneidölen, Hydraulikölen, insbesondere für den Bergbau, Trafoölen u. ä. enthalten, weil die Öle hierdurch unbrennbar werden. Andererseits ist das PCB mikrobiologisch nicht abbaubar, persistent und ubiquitär; es hat eine ähnliche Struktur wie DDT (Dichlordiphenyltrichlorethan) und wird auch in der Nahrungskette, wie in Fischen, in der Muttermilch und dgl. zunehmend aufgefunden. In dieser oder ähnlicher Weise kontaminierte Altöle, die mehr als 20 mg/kg PCB und/oder mehr als 0,5 Gew.-% Organochlorverbindungen enthalten, gelten als Abfall und unterliegen damit den Vorschriften über Abfallbesei­tigung. Die Höchstgrenzen werden in Zukunft sogar noch weiter abgesenkt werden. Altöle mit einer Kontamination oberhalb dieser Werte müssen als Sonderabfall in einer dafür zugelassenen Son­derabfallbeseitungsanlage, z. B. einer Hochtemperaturverbren­nungsanlage entsorgt werden. Deren Kapazität in der Bundesre­publik Deutschland ist völlig unzureichend, so daß es schon zu Entsorgungsengpässen gekommen ist. Bei der Hochtemperaturver­brennung wird das Altöl bei Temperaturen oberhalb 1 200° C und Verweilzeiten von mehr als 0,3 sec verbrannt, wodurch die Entstehung von Giften, wie Dioxin, unterbunden wird.In the Federal Republic of Germany alone, around 500,000 t of waste oils are currently generated annually, which is about 50% of the fresh oil used in the same period. A large part of the waste oil is processed into so-called secondary refinements. The processing of waste oil into secondary refinements requires that the waste oil is contaminated only to a very small extent with components that lead to environmental damage when the secondary refinate is used. Organochlorine compounds, in particular PCB (polychlorinated biphenyls), are particularly disruptive; from these impurities, the highly toxic chlorinated dibenzodioxins and dibenzofurans can arise if the second raffinate, e.g. B. burns as lubricating oil in internal combustion engines at low temperature. Polychlorinated biphenyls are e.g. B. in cutting oils, hydraulic oils, especially for mining, transformer oils and. Ä. included, because this makes the oils incombustible. On the other hand, the PCB is non-biodegradable, persistent and ubiquitous; it has a structure similar to DDT (dichlorodiphenyltrichloroethane) and is also increasingly found in the food chain, such as in fish, in breast milk and the like. Waste oils contaminated in this or a similar way, which contain more than 20 mg / kg PCB and / or more than 0.5% by weight organochlorine compounds, are considered waste and are therefore subject to the regulations on waste disposal. The maximum limits will go even further in the future be lowered. Waste oils with contamination above these values must be disposed of as hazardous waste in an approved hazardous waste disposal facility, e.g. B. a high temperature incinerator. Their capacity in the Federal Republic of Germany is completely inadequate, so that there are already bottlenecks in disposal. In high-temperature combustion, the waste oil is burned at temperatures above 1,200 ° C and residence times of more than 0.3 seconds, which prevents the formation of poisons such as dioxin.

Auch die Aufbereitung von nicht oder weniger kontaminierten Altölen ist problematisch. Bei dem hierfür an sich geeigneten Schwefelsäure-Bleicherde-Verfahren zur Erzeugung von Zweit­raffinaten entsteht ein Säureharz als ökologisch bedenklicher Rückstand.The treatment of non-contaminated or less contaminated waste oils is also problematic. In the sulfuric acid bleaching earth process, which is suitable per se for this purpose, for producing secondary raffinates, an acid resin is formed as an ecologically questionable residue.

Dieser Nachteil des Schwefelsäure-Bleicherde-Verfahrens wurde durch das KTI-Verfahren unterbunden, bei dem das Altöl zunächst einer physikalischen Behandlung und anschließend einem sogenann­ten Hydrofinishing unterzogen wird. Die physikalische Behand­lung besteht in einem mehrstufigen Reinigungsprozeß, bei dem zunächst unter atmosphärischem Druck und bei 150° C Wasser und leicht flüchtige Komponenten vom Altöl getrennt werden. Danach wird in einer zweiten Stufe bei einem Vakuum von 20 mbar und 270° C eine Gasölfraktion abgetrennt. Hieran schließt sich als dritte Stufe eine Hochvakuum-Kurzweg-Destillation an, die in einem besonderen Dünnschichtverdampfer bei 310° C und einem Vakuum von 2 mbar unter Anwendung indirekter Wärmeüber­tragung bei gleichzeitiger hoher Turbulenz in den Wärmeübergangs­zonen stattfindet. Hierdurch werden schwere Bestandteile des Altöls, die aus Additiven, Metallen und Zersetzungsprodukten bestehen, als asphaltartiger Rückstand abgetrennt. Als vierte Stufe schließt sich das Hydrofinishing an, bei dem nur noch solche Verunreinigungen in der gereinigten Ölfraktion enthalten sind, die den gleichen Siedebereich wie die gereinigte Ölfraktion selbst haben - es handelt sich hauptsächlich um chlor-, sauer-­stoff- und stickstoffhaltige Komponenten. Das Hydrofinishing erfolgt bei Drücken von etwa 50 bar und Temperaturen zwischen 300 und 350° C, wobei die Verunreinigungen als Ammoniumchlorid, Gasöl und Wasser abgetrennt und evtl. vorhandene Schwefelverun­reinigungen als H₂S entfernt werden. Die Anwesenheit von Or­ganochlorverbindungen oder Äthylenglykolen (aus Frostschutz­mitteln) haben jedoch negative Folgen, indem sie den Wasserstoff­verbrauch erhöhen, die Katalysatoren schneller kontaminieren und darüber hinaus die Verwendung spezieller Katalysatoren erforderlich machen.This disadvantage of the sulfuric acid bleaching earth process was prevented by the CTI process, in which the waste oil is first subjected to a physical treatment and then to a so-called hydrofinishing. The physical treatment consists of a multi-stage cleaning process in which water and highly volatile components are first separated from the waste oil under atmospheric pressure and at 150 ° C. A gas oil fraction is then separated off in a second stage at a vacuum of 20 mbar and 270 ° C. This is followed by a third stage, a high-vacuum short-path distillation, which takes place in a special thin-film evaporator at 310 ° C and a vacuum of 2 mbar using indirect heat transfer with simultaneous high turbulence in the heat transfer zones. As a result, heavy components of the waste oil, which consist of additives, metals and decomposition products, are separated as asphalt-like residues. The fourth stage is followed by hydrofinishing, in which only such impurities are contained in the purified oil fraction that have the same boiling range as the purified oil fraction itself - they are mainly components containing chlorine, oxygen and nitrogen. The hydrofinishing takes place at pressures of about 50 bar and temperatures between 300 and 350 ° C, the impurities being separated off as ammonium chloride, gas oil and water and any sulfur impurities present being removed as H₂S. However, the presence of organochlorine compounds or ethylene glycols (from anti-freeze) have negative consequences in that they increase hydrogen consumption, contaminate the catalysts more quickly and, moreover, require the use of special catalysts.

Davon ausgehend liegt der Erfindung die Aufgabe zugrunde, ein Verfahren zum hydrierenden Aufbereiten von Altölen zu Zweit­raffinaten, insbesondere in Form von Schmierölen, unter Vermei­dung ökologisch unerwünschter Nebenprodukte oder Abfälle zu erhalten, mit dem es insbesondere möglich ist, auch solche Altöle aufzubereiten, die bisher, insbesondere aufgrund ihres Gehaltes an Organochlorverbindungen und insbesondere des PCB, nur durch Sonderabfallbeseitigungsanlagen entsorgt werden konn­ten.Proceeding from this, the object of the invention is to obtain a process for the hydrogenative treatment of waste oils to give secondary refinates, in particular in the form of lubricating oils, while avoiding ecologically undesirable by-products or wastes, with which it is possible in particular to also treat waste oils which previously, especially due to their content of organochlorine compounds and in particular the PCB, could only be disposed of by special waste disposal plants.

Diese Aufgabe wird erfindungsgemäß durch ein Verfahren der eingangs genannten Art gelöst, bei dem das Altöl zunächst von groben Feststoffen befreit und nachfolgend einer Hy­drierung in einer Sumpfphase bei Drücken von 30 bis 300, vorzugs­weise 150 bar und Temperaturen von 200 bis 450, vorzugsweise 350° C, unterzogen wird und sodann eine Trennung der Reaktions­produkte in das Schmieröl und Nebenprodukte erfolgt.This object is achieved according to the invention by a process of the type mentioned at the outset, in which the waste oil is first freed of coarse solids and subsequently hydrogenated in a sump phase at pressures of 30 to 300, preferably 150 bar and temperatures of 200 to 450, preferably 350 ° C. , is subjected and then a separation of the reaction products into the lubricating oil and by-products takes place.

Durch die Erfindung werden u. a. folgende Vorteile erzielt:
-Im Gegensatz zur Hochtemperaturverbrennung, bei der die Öle vernichtet werden, können die durch die Erfindung im Wege der hydrierenden Dechlorierung erzeugten Produkte als Zweit­raffinate einer volkswirtschaftlich sinnvollen Wiederverwendung zugeführt werden;
- die typischen Produkteigenschaften der Schmieröle bleiben erhalten;
- das Verfahren kann auch zur hydrierenden Aufarbeitung nicht kontaminierter Öle eingesetzt werden, ohne daß ökologisch schädliche oder bedenkliche, also insgesamt ökologisch uner­wünschte Nebenprodukte oder Abfälle entstehen, wie sie vom Schwefelsäure-Bleicherde-Verfahren bekannt sind;
- aus dem Altöl können sogenannte Alterungsprodukte des Öles sowie auch Additive nach dem Hydrierungsschritt in der Sumpf­phase problemlos entfernt werden;
- die Trennung in Rückstände und Produktöl ist bei gleichzei­tiger Verwendbarkeit relativ preiswerter Katalysatoren weniger aufwendig als nach bekannten Verfahren, z. B. dem KTI-Verfah­ren.The following advantages are achieved by the invention:
In contrast to high-temperature combustion, in which the oils are destroyed, the products produced by the invention by means of hydrogenating dechlorination can be reused as economically useful reuse.
- The typical product properties of the lubricating oils are retained;
- The process can also be used for the hydrogenative work-up of uncontaminated oils without producing ecologically harmful or questionable, that is to say ecologically undesirable, by-products or wastes, as are known from the sulfuric acid bleaching earth process;
- So-called aging products of the oil as well as additives can be removed from the waste oil after the hydrogenation step in the sump phase without any problems;
- The separation into residues and product oil is at the same time usability of relatively inexpensive catalysts less expensive than by known methods, eg. B. the CTI procedure.

Unter "Altölen", "Zweitraffinaten", "Befreiung von groben Fest­stoffen" sowie "Hydrierung in der Sumpfphase" ist im Sinne der Erfindung folgendes zu verstehen:For the purposes of the invention, “waste oils”, “secondary refinates”, “removal of coarse solids” and “hydrogenation in the bottom phase” mean the following:

Altöle im Sinne dieser Erfindung sind Öle, die infolge ihres durch den bisherigen Gebrauch bedingten Zustandes nicht mehr bestimmungsgemäß verwendet werden können. Neben den durch den natürlichen Verschleiß und Alterung anfallenden Fremdstoffen können auch halogenhaltige Verunreinigungen im Öl enthalten sein. Waste oils in the sense of this invention are oils which, due to their condition due to previous use, can no longer be used as intended. In addition to the foreign substances resulting from natural wear and aging Halogen-containing impurities can also be contained in the oil.

Zweitraffinate sind Produkte, die nach Anwendung des erfindungs­gemäßen Verfahrens und nach Zugabe von üblichen Additiven als Schmieröle wiederverwendet werden können. Secondary refinates are products that can be reused as lubricating oils after the method according to the invention has been applied and after the addition of conventional additives.

Befreiung von groben FeststoffenRelief from coarse solids

Für den Einsatz des Verfahrens ist es notwendig, die Öle von solchen Feststoffen wie Putzlappen, Handschuhe, grobe Metall­späne etc. zu befreien, um Störungen z. B. an Pumpen oder Ent­spannungsventilen zu vermeiden.For the use of the method, it is necessary to free the oils from such solids as cleaning rags, gloves, coarse metal shavings, etc. B. to avoid pumps or expansion valves.

Hydrierung in der SumpfphaseHydrogenation in the bottom phase

Beim Hydrieren in der Sumpfphase befindet sich das Altöl im Reaktionsraum im flüssigen Zustand.During hydrogenation in the bottom phase, the waste oil is in the liquid state in the reaction space.

Gemäß einer Weiterbildung der Erfindung erfolgt die Hydrierung in der Sumpfphase, vorzugsweise in Gegenwart eines schwach hydrieraktiven Katalysators. Hierzu zählen insbesondere Fe-Kata­lysatoren, wie Bayermasse (Rotschlamm) oder mit Eisensalzen getränkte Trägermaterialien.According to a development of the invention, the hydrogenation takes place in the bottom phase, preferably in the presence of a weakly hydrogenation-active catalyst. These include, in particular, Fe catalysts, such as Bavarian mass (red mud) or support materials impregnated with iron salts.

Wenn, gemäß einer anderen Weiterbildung der Erfindung, die Hydrierung in der Sumpfphase unter Zugabe eines Neutralisations­mittels, insbesondere eines Na-Salzes einer schwachen Säure, wie Natriumsulfid, erfolgt, können auch stärker kontaminierte Altöle, d. h. solche mit relativ hohem Gehalt an Organochlor­verbindungen zu Zweitraffinaten in Form von Schmierölen aufberei­tet werden, ohne daß ökologisch bedenkliche oder schädliche Neben- oder Abfallprodukte entstehen. Die Zugabe des Neutra­lisationsmittels erfolgt vorzugsweise vor Zugabe des Wasserstof­fes, insbesondere gemeinsam mit einem Katalysator. Typische Zugabemengen betragen zwischen der ein- bis dreifachen stöchio­metrischen Menge, bezogen auf Chlor im eingesetzten Altöl.If, according to another development of the invention, the hydrogenation takes place in the bottom phase with the addition of a neutralizing agent, in particular a Na salt of a weak acid, such as sodium sulfide, more contaminated waste oils, ie those with a relatively high content of organochlorine compounds, can also be used as secondary raffinates Form of lubricating oils are prepared without producing environmentally harmful or harmful by-products or waste products. The neutralizing agent is preferably added before the hydrogen is added, in particular together with a catalyst. Typical The amounts added are between one and three times the stoichiometric amount, based on chlorine in the used oil.

Die Trennung der Reaktionsprodukte der Hydrierung in der Sumpf­phase in das Schmieröl bzw. ein Vorprodukt des Schmieröles einerseits und in Nebenprodukte andererseits erfolgt in einem Heißabscheider, in dem ein die Gase enthaltendes Kopfprodukt von einem die gesamten Flüssigkeiten und Feststoffe enthaltenden Sumpfprodukt getrennt werden. Ein solcher Heißabschneider wird in der Regel bei etwa 30 bis 50° C unter der Temperatur im Sumpfphasenreaktor betrieben.The separation of the reaction products of the hydrogenation in the bottom phase into the lubricating oil or a preliminary product of the lubricating oil on the one hand and in by-products on the other hand takes place in a hot separator in which a top product containing the gases is separated from a bottom product containing all liquids and solids. Such a hot cutter is usually operated at about 30 to 50 ° C below the temperature in the bottom phase reactor.

Gemäß einer anderen Weiterbildung der Erfindung wird das Sumpf­produkt des Heißabscheiders vorzugsweise in einer Vakuumkolonne destilliert. Der dabei anfallende Vakuumrückstand enthält als Feststoffe insbesondere den Katalysator und Natriumchlorid, das sich aus der Dechlorierung von Organochlorverbindungen gebildet hat. Überraschenderweise ist es nämlich durch die Erfindung möglich, das Chlor aus besonders problematischen Organochlorverbindungen wie das PCB, chlorierte Dioxine und Dibenzofurane in ökologisch völlig unbedenkliches Natriumchlorid vollständig umzuwandeln und abzuscheiden. Die Kopfprodukte der Vakuumkolonne und des Heißabscheiders werden bevorzugt zur Gewinnung des Schmieröles vereinigt.According to another development of the invention, the bottom product of the hot separator is preferably distilled in a vacuum column. The resulting vacuum residue contains, as solids, in particular the catalyst and sodium chloride, which has formed from the dechlorination of organochlorine compounds. Surprisingly, it is in fact possible through the invention to completely convert and separate the chlorine from particularly problematic organochlorine compounds such as the PCB, chlorinated dioxins and dibenzofurans into ecologically completely harmless sodium chloride. The top products of the vacuum column and the hot separator are preferably combined to obtain the lubricating oil.

Eine dem Trennschritt der festen Reaktionsprodukte aus der Hydrierung in der Sumpfphase von den flüssigen Reaktionsprodukten nachgeschaltete Hydrierung in der Gasphase führt zu einer Qua­litätsverbesserung des zu gewinnenden Zweitraffinates in Form von Schmierölen. Unter einer "Hydrierung in der Gasphase" ist im Sinne der Erfindung eine Hydrierung der flüssig oder dampf­förmig vorliegenden Öle an einem Raffinationskatalysator zu verstehen. Als Raffinationskatalysatoren werden bevorzugt Nickel/­Molybdän- bzw. Kobalt/Molybdän-KatalysatorenA hydrogenation in the gas phase following the separation step of the solid reaction products from the hydrogenation in the bottom phase from the liquid reaction products leads to an improvement in the quality of the secondary raffinate to be obtained in the form of lubricating oils. For the purposes of the invention, “hydrogenation in the gas phase” is understood to mean hydrogenation of the liquid or vaporous oils over a refining catalyst. Nickel / molybdenum or cobalt / molybdenum catalysts are preferred as refining catalysts

Das von groben Feststoffen, insbesondere durch Filtration befrei­te Altöl mit einem Organochlorgehalt von 0,6 Gew.-% wird zusammen mit 3 Gew.-% Bayermasse als Katalysator und 2,7 % Na₂S (2-fach stöchiometrische Menge) als Neutralisationsmittel eingesetzt. Nach Zugabe Von 1000 1 Wasserstoff je kg Altöl wird das zu hydrierende Gemisch vor Einspeisung in den Sumpfphasenreaktor 2 in einem Vorheizer 1 bei 150 bar auf 350° C erhitzt und an­schließend im Sumpfphasenreaktor 2 bei 150 bar und 350° C hy­driert.The coarse solids, in particular by filtration, used oil with an organochlorine content of 0.6 wt .-% is used together with 3 wt .-% Bavarian mass as a catalyst and 2.7% Na₂S (2-fold stoichiometric amount) as a neutralizing agent. After adding 1000 l of hydrogen per kg of waste oil, the mixture to be hydrogenated is heated to 350 ° C. in a preheater 1 at 150 bar before being fed into the bottom phase reactor 2 and then hydrogenated in the bottom phase reactor 2 at 150 bar and 350 ° C.

Die Reaktionsprodukte aus der Hydrierung in der Sumpfphase werden in einem Heißabscheider 3 getrennt, wobei die dampfförmig vorliegenden Produkte über Kopf, die Flüssigphase und die Fest­stoffe als Sumpfprodukt am unteren Ende des Heißabscheiders 3 abgezogen werden.The reaction products from the hydrogenation in the bottom phase are separated in a hot separator 3, the vaporous products being taken off overhead, the liquid phase and the solids as bottom product at the lower end of the hot separator 3.

Das aus dem Heißabscheider 3 abgezogene Sumpfprodukt wird in einer Vakuumdestillationskolonne 4 bei Temperaturen von 350° C und Drücken von 20 mbar in ein flüssiges Kopfprodukt und in einen möglichst noch pumpfähigen, die Feststoffe enhaltenden Vakuumrückstand getrennt. Dabei werden die in der Hydrierung in der Sumpfphase als Chlor abgespaltenen und als Natriumchlo­rid gebundenen Organochlorverbindungen sowie in dem Altöl ent­haltene Additive und Alterungsprodukte abgetrennt. Die Kopf­produkte aus dem Heißabscheider 3 und der Vakuumdestillationsko­lonne 4 werden nachfolgend in einem Gasphasereaktor 5 unter folgenden Arbeitsbedingungen hydriert:
    Druck      100 bar
    Temperatur      350° C
Als Katalysator wird ein Nickel/Molybdän-Katalysator auf - Al₂O₃ eingesetzt.The bottom product withdrawn from the hot separator 3 is separated in a vacuum distillation column 4 at temperatures of 350 ° C. and pressures of 20 mbar into a liquid top product and into a vacuum residue which is still pumpable and contains the solids if possible. The organochlorine compounds split off as chlorine in the bottom phase in the hydrogenation and bound as sodium chloride, as well as additives and aging products contained in the waste oil, are separated off. The top products from the hot separator 3 and the vacuum distillation column 4 are subsequently hydrogenated in a gas phase reactor 5 under the following working conditions:
Pressure 100 bar
Temperature 350 ° C
As a catalyst, a nickel / molybdenum catalyst is used on - Al₂O₃.

In einem dem Gasphasereaktor 5 nachgeschalteten Kaltabscheider 6 wird bei Temperaturen von etwa 300° C und Drücken von 100 bar das Reaktionsprodukt der Hydrierung in flüssige und gasförmige Bestandteile getrennt. Das anfallende Gas, vorzugsweise Wasser­stoff, wird nach Gasreinigung recyclisiert. Die Flüssigphase wird entspannt und das Produktöl abgezogen.In a cold separator 6 downstream of the gas phase reactor 5, the reaction product of the hydrogenation is separated into liquid and gaseous components at temperatures of approximately 300 ° C. and pressures of 100 bar. The resulting gas, preferably hydrogen, is recycled after gas cleaning. The liquid phase is relaxed and the product oil is drawn off.

Aus 1 kg eine Altöles wurden auf diese Weise 0,8 kg eines chlor­freien Öles gewonnen, das nach Zugabe von Additiven als Schmieröl verwendet werden kann.In this way, 0.8 kg of a chlorine-free oil was obtained from 1 kg of waste oil, which can be used as a lubricating oil after the addition of additives.

Claims (8)

1. Verfahren zum hydrierenden Aufarbeiten von Altölen zu Zweit­raffinaten in Form von Schmierölen unter Zugabe von Wasser­stoff, dadurch gekennzeichnet, daß das Altöl zunächst von groben Feststoffen befreit und nachfolgend einer Hydrierung in einer Sumpfphase bei Drücken von 30 bis 300 bar und Temperaturen von 200 bis 450° C unterzogen wird und sodann eine Trennung der Reaktionsprodukte in das Schmier­öl und Nebenprodukte erfolgt.1. A process for the hydrogenation of waste oils to give secondary raffinates in the form of lubricating oils with the addition of hydrogen, characterized in that the waste oil is first freed of coarse solids and subsequently hydrogenated in a sump phase at pressures of 30 to 300 bar and temperatures of 200 to 450 ° C is subjected and then a separation of the reaction products into the lubricating oil and by-products takes place. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Hydrierung in der Sumpfphase in Gegenwart eines gering hy­drieraktiven Katalysators erfolgt.2. The method according to claim 1, characterized in that the hydrogenation takes place in the bottom phase in the presence of a low hydrogenation catalyst. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Hydrierung in der Sumpfphase unter Zugabe eines Neutralisationsmittels erfolgt.3. The method according to claim 1 and 2, characterized in that the hydrogenation takes place in the bottom phase with the addition of a neutralizing agent. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn­zeichnet, daß die Reaktionsprodukte aus der Hydrierung in der Sumpfphase in einem Heißabscheider in ein Flüssigkeiten und Feststoffe enthaltendes Sumpfprodukt und ein dampfförmiges Kopfprodukt getrennt werden.4. The method according to any one of claims 1 to 3, characterized in that the reaction products from the hydrogenation in the bottom phase are separated in a hot separator into a bottom product containing liquids and solids and a vaporous top product. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Sumpfprodukt in einer Vakuumkolonne destilliert wird.5. The method according to claim 4, characterized in that the bottom product is distilled in a vacuum column. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Kopfprodukte von Vakuumkolonne und Heißabscheider vor der Gewinnung des Schmieröles vereinigt werden.6. The method according to claim 5, characterized in that the top products of the vacuum column and hot separator are combined before the extraction of the lubricating oil. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekenn­zeichnet, daß die flüssigen Reaktionsprodukte aus der Hy­drierung in der Sumpfphase in der Gasphase bei Drücken von 50 bis 200 bar und Temperaturen von 300 bis 400° C an Raffinationskatalysatoren hydriert werden.7. The method according to any one of claims 1 to 6, characterized in that the liquid reaction products from the hydrogenation in the bottom phase are hydrogenated in the gas phase at pressures of 50 to 200 bar and temperatures of 300 to 400 ° C on refining catalysts. 8. Verfahren nach Anspruch 7, dadurch gekenn­zeichnet, daß als Raffinationskatalysatoren Nickel/Molybdän- und Kobalt-Molybdän-Katalysatoren verwendet werden.8. The method according to claim 7, characterized in that nickel / molybdenum and cobalt-molybdenum catalysts are used as refining catalysts.
EP88105856A 1987-07-17 1988-06-23 Process for working up used lubricants by hydrogenation Withdrawn EP0299149A3 (en)

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DE19873723607 DE3723607A1 (en) 1987-07-17 1987-07-17 METHOD FOR HYDROGENATING WORKOUT OF ALTOELS

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JPS6436694A (en) 1989-02-07
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EP0299149A3 (en) 1989-03-08

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