EP0228651B1 - Process for obtaining high-grade lubricants from spent oils - Google Patents

Process for obtaining high-grade lubricants from spent oils Download PDF

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Publication number
EP0228651B1
EP0228651B1 EP86117551A EP86117551A EP0228651B1 EP 0228651 B1 EP0228651 B1 EP 0228651B1 EP 86117551 A EP86117551 A EP 86117551A EP 86117551 A EP86117551 A EP 86117551A EP 0228651 B1 EP0228651 B1 EP 0228651B1
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Prior art keywords
oils
oil
waste
boiling
hydrogen
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French (fr)
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EP0228651A1 (en
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Karl-Heinz Keim
Hartmut Dr. Hammer
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RWE Entsorgung AG
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RWE Entsorgung 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

Definitions

  • the invention relates to a process for the catalytic hydrogenating treatment of waste oils or mixtures containing waste oil at elevated pressure and temperature while reducing the portion boiling> 350 ° C. by 20-70%.
  • waste oils includes all waste oils such as used spindle oils, machine oils, lubricants for motors and gears, cylinder oils, metalworking oils, hydraulic oils, industrial waste oils, etc.
  • Waste oils are used oils that can no longer be used as such.
  • Waste oils mainly consist of a base oil based on mineral oil or synthetic oil, but some contain considerable amount of foreign matter, e.g. Water, solvents, fuels, asphalt-like substances, acids, resins, ashes and additives, such as antioxidants, anti-corrosion agents, wetting agents, dispersants, anti-foaming agents, viscosity index improvers, etc.
  • the additives can contain halogens, sulfur and nitrogen compounds, and numerous other partially toxic components.
  • Common synthetic lubricating oils are, for example, polyether oils (e.g. polyethylene glycol, polypropylene glycol or mixed polyolefin glycols), ester oils, silicone oils, oils from chlorinated or fluorinated hydrocarbons, etc.
  • used oils are generally not stored and stored separately according to their origin, but mostly from mixtures of e.g. Motor oils based on mineral oils, machine oils, synthetic oils, transformer oils etc. consist. Mixtures of the latter oils can lead to the formation of highly toxic dioxins during combustion.
  • a known second refining process is, for example, the sulfuric acid bleaching earth hot contact process, in which after atmospheric drying to 0.12% water content, about 11-13% by weight sulfuric acid is added to the waste oil and passed into settling tanks. After 24-48 hours, additional treatment is carried out with bleaching earth (waste oil recycling, K. Müller, Erich Schmidt Verlag GmbH, Berlin, 1982, p. 89).
  • the refining hydrogenation according to this process takes place after several pretreatment steps at 200-430 ° C., preferably at 360 ° C. and a pressure of 10.2-206.7 bar, preferably 50.3 bar (US Pat. No. 4,151,072, FIG. 1 ).
  • PROP process also at least partially degrades polychlorobiphenyls (Hydrocarbon Processing, Sept. 1979, p. 152, right column, lines 43-51), chlorinated solvents and cleaning fluids, metalworking oils, other working fluids as well as insulating and transformer oils undesirable as feedstocks in the PROP process. Suitable products for the PROP process are therefore essentially used engine oils.
  • KTI Karl Fischer Scientific ° C
  • vacuum distillation is carried out at 26 mbar and 270 ° C.
  • high-vacuum distillation takes place at 310 ° C and 2.6 mbar, which is designed as thin-film evaporation.
  • the product is then subjected to hydrogenating refining at 50 bar and 300-350 ° C.
  • a solution to this problem is disclosed by the present invention, which permits the production of high-quality lubricants with a high viscosity index and the production of valuable feedstock for ethylene plants by catalytic hydrogenation treatment of solids, if applicable, and other dissolved substances and / or emulsified additives and water and, if necessary, chemically and / or physically pretreated waste oils or mixtures containing waste oils with hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, characterized in that the hydrogenating treatment is carried out in the presence of a ( of) commercial hydrocracking catalyst (s) at temperatures of 350-480 ° C, pressures of 20-400 bar, an LHSV of 2-20 1 / 1 ⁇ h, and that the portion with boiling points> 350 ° C 20-70% reduced.
  • a commercial hydrocracking catalyst s
  • Lubricants with a high viscosity index can be obtained.
  • a further advantageous effect of the process according to the invention is the degradation of the synthetic lubricants contained in waste oil, such as the ester lubricants, the polyalkylene glycols, silicone lubricants, lubricants containing sulfur and others.
  • a particularly valuable lubricating oil product which consists practically entirely of hydrocarbons and, in addition to being used as a lubricant, is also outstandingly suitable for use as an ethylene feed, with over 30% by weight of ethylene being obtainable.
  • the hydrocarbons obtained in the gasoline and medium oil boiling range can also be used as ethylene feed.
  • both zeolitic and amorphous catalysts can be used as hydrocracking catalysts.
  • the active hydrocracking components can be, for example, Ni / Mo, Ni / W, Co / Mo, Co / W or mixtures thereof, but also other metals or metal compounds, for example from sub-group VIII to VIII of the periodic table. Accordingly, in the method according to the invention, for example, all are state of the art suitable hydrocracking catalysts.
  • amorphous hydrocracking catalysts are preferred, which according to the prior art, for example, aluminum silicates, SiO2, Al2O3, etc. May contain oxides as a base.
  • zeolitic catalysts yield comparable results in terms of yield and viscosity index, but that in the presence of amorphous catalysts there is practically no increase in the pour point, whereas in the presence of crystalline, zeolitic catalysts there is a sharp increase in the pour point are observed, so that when the products are used as lubricating oil in the latter case dewaxing is required. If the products according to the invention are used as ethylene feed, the pour point has only a minor influence.
  • refining catalysts can optionally also be used according to the invention under more stringent conditions than gap catalysts.
  • the catalysts are used according to the invention as fixed bed catalysts, but the results according to the invention are also obtained when using the fluidized bed or fluidized bed process. Methods can also be used in which the catalyst is in suspension.
  • the feed product to be treated according to the invention is reacted with hydrogen, hydrogen-containing gases, which may additionally contain, for example, N2, CO2, hydrocarbons and other admixtures or mixed with hydrogen-transferring solvents at temperatures from 350 to 480 ° C., pressures from 20 to 400 bar and an LHSV of 2 to 20 l / h ⁇ l, the conditions being set depending on the feed product so that the proportion in the feed oil with a boiling point> 350 ° C. is reduced by 20 to 70%.
  • hydrogen-containing gases which may additionally contain, for example, N2, CO2, hydrocarbons and other admixtures or mixed with hydrogen-transferring solvents at temperatures from 350 to 480 ° C., pressures from 20 to 400 bar and an LHSV of 2 to 20 l / h ⁇ l, the conditions being set depending on the feed product so that the proportion in the feed oil with a boiling point> 350 ° C. is reduced by 20 to 70%.
  • the process is preferably carried out at a temperature of 400 to 460 ° C, a pressure of 100 to 350 bar and an LHSV of 4 - 12 l / h ⁇ l and the proportion in the feed oil with a boiling point> 350 ° C is reduced by 30 - 60%.
  • the hydrogenation temperature can also be a temperature profile e.g. be a sawtooth profile.
  • the splitting hydrogenating treatment is preferred, in particular when using crystalline zeolite catalysts, before a refining step.
  • the catalyst volume of the refining stage usually corresponds approximately to that of the hydrocracking stage. However, depending on the composition of the feed oil, changes in the volume ratios are possible within wide limits, for example from 5: 1 to 1: 5. Commercial products can be used as refining catalysts. Furthermore, as already explained above, a stage for removing metals can be installed.
  • a catalyst which has both refining and cleavage properties preferably two separate catalyst beds which are operated under different conditions, in particular at a higher temperature in the cracking stage.
  • Lubricating oils are obtained which are free from oxygen, halogen, nitrogen, sulfur and metals and have viscosity index values (VI) of 110 to 130, good to high yields being obtained depending on the viscosity index.
  • the used waste oils can also contain, for example, synthetic oils based on polyether, polyglycol, polyester, polychlorobiphenyls, etc. or small proportions of oils with a viscosity index ⁇ 90, such as transformer oils. If necessary. can also be mixed with crude oil, residual oil from mineral or coal origins and similar oils, such as from oil shale, oil sands and the like, with dewaxing being added if necessary.
  • HVI high viscosity index
  • the conditions according to the invention additionally lead to the almost complete degradation of the compounds with hetero elements in the feed product.
  • chlorine-containing compounds are no longer detectable in the lubricant product, and sulfur and nitrogen compounds, which for example derive from the added dissolved additives, are almost completely broken down.
  • the products obtained under the conditions according to the invention are also outstandingly suitable as feeds for use in ethylene plants.
  • temperature, pressure and residence time have to be adjusted accordingly.
  • Example 2 The experiment according to Example 1 was repeated, but the process was carried out at 440 ° C. and the portion boiling> 350 ° C. was reduced to 60%. 30% of an ester oil-free lubricating oil were obtained with a viscosity index of 125 and a boiling range> 400 ° C. Similar results were obtained with different refining upstream.
  • Pre-cleaned and distilled waste oil with a proportion of 3% by weight of polyalkylene glycol lubricating oil was reacted with a 20% degradation over a boiling portion> 350 ° C. over an amorphous catalyst. 73% of a> 400 ° C. boiling polyalkylene glycol-free lubricating oil with a viscosity index of 110 were obtained.
  • Example 5 was repeated, the feed oil containing 6000 ppm polychlorobiphenyl (PCB). ⁇ 1 ppm PCB was found in the product.
  • the pre-cleaning should be selected so that the catalyst is not damaged or only slightly damaged or is inactivated little by impurities. Suitable measures must therefore be taken depending on the used oil from the state of the art.

Abstract

Spent oils or mixtures containing spent oil are treated by catalytic hydrogenation at elevated pressure and elevated temperature with a 20 - 70 % reduction of the fraction boiling at 350 DEG C.

Description

Die Erfindung betrifft ein Verfahren zur katalytischen hydrierenden Behandlung von Altölen oder Altöl enthaltenden Gemischen bei erhöhtem Druck und erhöhter Temperatur unter Verringerung des > 350°C siedenden Anteils um 20 - 70%.The invention relates to a process for the catalytic hydrogenating treatment of waste oils or mixtures containing waste oil at elevated pressure and temperature while reducing the portion boiling> 350 ° C. by 20-70%.

Unter den Begriff "Altöle" fallen alle Abfallöle wie beispielsweise verbrauchte Spindelöle, Maschinenöle, Schmierstoffe für Motoren und Getriebe, Zylinderöle, Metallbearbeitungsöle, Hydrauliköle, Industrieabfallöle, u.a.The term "waste oils" includes all waste oils such as used spindle oils, machine oils, lubricants for motors and gears, cylinder oils, metalworking oils, hydraulic oils, industrial waste oils, etc.

Bei den Altölen handelt es sich um verbrauchte Öle, die als solche nicht mehr weiter verwendet werden können. Altöle bestehen überwiegend aus einem Grundöl auf Mineralöl- oder Syntheseölbasis, enthalten jedoch einen z.T. erheblichen Fremdstoffanteil, z.B. Wasser, Lösungsmittel, Kraftstoffe, asphaltartige Stoffe, Säuren, Harze, Aschen und Additive, wie Antioxidantien, Korrosionsschutzmittel, Netzmittel, Dispergiermittel, Schaumverhütungsmittel, Viskositätsindexverbesserer u.a. Die Additive können Halogene, Schwefelund Stickstoffverbindungen und zahlreiche andere teilweise toxische Komponenten enthalten. Übliche synthetische Schmieröle sind beispielsweise Polyetheröle, (z.B. Polyethylenglykol, Polypropylenglykol oder Mischpolyolefinglykole), Esteröle, Silikonöle, Öle aus chlorierten oder fluorierten Kohlenwasserstoffen u.a.The waste oils are used oils that can no longer be used as such. Waste oils mainly consist of a base oil based on mineral oil or synthetic oil, but some contain considerable amount of foreign matter, e.g. Water, solvents, fuels, asphalt-like substances, acids, resins, ashes and additives, such as antioxidants, anti-corrosion agents, wetting agents, dispersants, anti-foaming agents, viscosity index improvers, etc. The additives can contain halogens, sulfur and nitrogen compounds, and numerous other partially toxic components. Common synthetic lubricating oils are, for example, polyether oils (e.g. polyethylene glycol, polypropylene glycol or mixed polyolefin glycols), ester oils, silicone oils, oils from chlorinated or fluorinated hydrocarbons, etc.

Es ist allgemein bekannt, daß es aufgrund der großen Mengen anfallenden Altöls von erheblichem wirtschaftlichem Interesse ist, aus diesen wiederverwendbare Produkte zu gewinnen.It is generally known that it is of considerable economic interest to obtain reusable products from the large amounts of waste oil produced.

Die Wiederaufarbeitung von Altölen wird als Zweitraffination bezeichnet. Die dem Stand der Technik entsprechenden Verfahren sind insbesondere in jüngster Zeit auf erhebliche öffentliche Kritik gestoßen, da Altöle im allgemeinen nicht entsprechend ihrer Herkunft gesondert gelagert und aufbewahrt werden, sondern meist aus Gemischen von z.B. Motorenölen auf Mineralölbasis, Maschinenölen, synthetischen Ölen, Transformatorenölen u.a. bestehen. Beimengungen letzterer Öle können bei der Verbrennung zur Bildung hochgiftiger Dioxine führen.The reprocessing of used oils is referred to as secondary refining. The methods corresponding to the state of the art have met with considerable public criticism in particular recently, since used oils are generally not stored and stored separately according to their origin, but mostly from mixtures of e.g. Motor oils based on mineral oils, machine oils, synthetic oils, transformer oils etc. consist. Mixtures of the latter oils can lead to the formation of highly toxic dioxins during combustion.

Ein bekanntes Zweitraffinations-Verfahren ist beipielsweise das Schwefelsäure-Bleicherde-Heißkontakt-Verfahren, bei dem das Altöl nach atmosphärischer Trocknung auf 0,12 % Wassergehalt mit ca. 11-13 Gew.% Schwefelsäure versetzt und in Absetzbehälter geleitet wird. Nach 24 - 48 Stunden wird zusätzlich mit Bleicherde behandelt (Altölverwertung, K. Müller, Erich Schmidt Verlag GmbH, Berlin, 1982, S 89).A known second refining process is, for example, the sulfuric acid bleaching earth hot contact process, in which after atmospheric drying to 0.12% water content, about 11-13% by weight sulfuric acid is added to the waste oil and passed into settling tanks. After 24-48 hours, additional treatment is carried out with bleaching earth (waste oil recycling, K. Müller, Erich Schmidt Verlag GmbH, Berlin, 1982, p. 89).

Auch die hydrierende Raffination von Altölen ist bekannt. So erfolgt beispielsweise im PROP-Verfahren der Phillips Company nach Vorbehandlung mit einer wässrigen Diammoniumphosphatlösung eine raffinierende Hydrierung über Nickel-Molybdän-Katalysatoren (US-PS 3,879,282, US-PS 3,930,988, US-PS 4,151,072: Hydrocarbon Processing, Sept. 1979, S.149).The hydrogenating refining of waste oils is also known. For example, in the Phillips Company's PROP process, after pretreatment with an aqueous diammonium phosphate solution, there is a refining hydrogenation over nickel-molybdenum catalysts (US Pat. No. 3,879,282, US Pat. No. 3,930,988, US Pat. No. 4,151,072: Hydrocarbon Processing, Sept. 1979, p. 149).

Die raffinierende Hydrierung gemäß diesem Verfahren erfolgt nach mehreren Vorbehandlungsstufen bei 200 - 430°C, vorzugsweise bei 360°C und einem Druck von 10,2 - 206,7 bar, vorzugsweise von 50,3 bar (US-PS 4,151,072, Fig.1).The refining hydrogenation according to this process takes place after several pretreatment steps at 200-430 ° C., preferably at 360 ° C. and a pressure of 10.2-206.7 bar, preferably 50.3 bar (US Pat. No. 4,151,072, FIG. 1 ).

Obgleich das PROP-Verfahren auch Polychlorbiphenyle zumindest teilweise abbaut (Hydrocarbon Processing, Sept. 1979, S. 152, rechte Spalte, Zeilen 43-51), sind chlorierte Lösungsmittel und Reinigungsflüssigkeiten, Metallbearbeitungsöle, andere Arbeitsflüssigkeiten sowie Isolier- und Transformatorenöle als Einsatzmaterialien im PROP-Verfahren unerwünscht. Für das PROP-Verfahren geeignete Einsatzprodukte sind daher im wesentlichen Alt-Motorenöle.Although the PROP process also at least partially degrades polychlorobiphenyls (Hydrocarbon Processing, Sept. 1979, p. 152, right column, lines 43-51), chlorinated solvents and cleaning fluids, metalworking oils, other working fluids as well as insulating and transformer oils undesirable as feedstocks in the PROP process. Suitable products for the PROP process are therefore essentially used engine oils.

Ein weiteres Verfahren mit einer hydrierenden Stufe ist das sog. KTI-Verfahren (Kinetics Technology International). Nach diesem Verfahren erfolgt nach Abtrennung leichtflüchtiger Komponenten, wie Benzin, Lösungsmitteln u.a., eine Vakuumdestillation bei 26 mbar und 270°C. In der nächsten Stufe erfolgt eine Hochvakuumdestillation bei 310°C und 2,6 mbar, die als Dünnschichtverdampfung ausgebildet ist. Das Produkt wird anschließend einer hydrierenden Raffination bei 50 bar und 300 - 350°C unterworfen.Another process with a hydrating stage is the so-called KTI process (Kinetics Technology International). According to this process, after the removal of volatile components such as gasoline, solvents etc., vacuum distillation is carried out at 26 mbar and 270 ° C. In the next stage, high-vacuum distillation takes place at 310 ° C and 2.6 mbar, which is designed as thin-film evaporation. The product is then subjected to hydrogenating refining at 50 bar and 300-350 ° C.

Die Verfahrensstufen machen für den Fachmann deutlich, daß dieses Verfahren mit sehr hohem technischem Aufwand verbunden ist, so daß die Wirtschaftlichkeit infrage gestellt ist (s. K. Müller, "Altölverwertung", Erich Schmidt Verlag, Berlin, 1982, s. 128 - 135, insbesondere S. 135, 2. Absatz).The process stages make it clear to the person skilled in the art that this process is associated with a very high technical outlay, so that the economic viability is questioned (see K. Müller, "Waste Oil Recycling", Erich Schmidt Verlag, Berlin, 1982, pp. 128-135) , in particular p. 135, 2nd paragraph).

Nach wie vor steht daher kein technisches Verfahren zur Verfügung, das die Aufarbeitung von Altölgemischen ermöglicht mit dem Ergebnis, wertvolle Produkte, insbesondere hochwertige Kohlenwasserstoff-Schmierstoffe mit hohem Viskositätsindex sowie als Einsatzstoffe für die Ethylenanlage verwendbare Produkte zu erzeugen, unter gleichzeitigem, vollständigem Abbau der Heteroelemente, insbesondere der Halogene, des Sauerstoffs, des Schwefels und Stickstoffs, das unter wirtschaftlich vertretbaren Bedingungen betreibbar ist.There is therefore still no technical process available that enables the processing of waste oil mixtures, with the result that valuable products, in particular high-quality hydrocarbon lubricants with a high viscosity index and products that can be used as feedstocks for the ethylene plant, are produced with simultaneous, complete degradation of the heterocouples , in particular the halogens, oxygen, sulfur and nitrogen, which can be operated under economically justifiable conditions.

Eine Lösung dieser Aufgabe offenbart die vorliegende Erfindung, welche die Gewinnung von hochwertigen Schmierstoffen mit hohem Viskositätsindex erlaubt sowie die Herstellung von wertvollem Einsatzprodukt für Ethylenanlagen durch katalytische hydrierende Behandlung von ggfs.von Feststoffen, sonstigen gelösten und/oder emulgierten Beimengungen und Wasser befreiten und ggfs. chemisch und/oder physikalisch vorbehandelten Altölen bzw. Altöle enthaltenden Gemischen mit Wasserstoff und/oder Wasserstoff enthaltenden Gasen und/oder Wasserstoff übertragenden Lösungsmitteln, dadurch gekennzeichnet, daß man die hydrierende Behandlung in Gegenwart eines (von) handelsüblichen Hydrocrack-Katalysators(en) bei Temperaturen von 350-480°C, Drücken von 20-400 bar, einer LHSV von 2-20 1/1`h durchführt, und daß man den Anteil mit Siedepunkte > 350°C um 20-70 % verringert.A solution to this problem is disclosed by the present invention, which permits the production of high-quality lubricants with a high viscosity index and the production of valuable feedstock for ethylene plants by catalytic hydrogenation treatment of solids, if applicable, and other dissolved substances and / or emulsified additives and water and, if necessary, chemically and / or physically pretreated waste oils or mixtures containing waste oils with hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, characterized in that the hydrogenating treatment is carried out in the presence of a ( of) commercial hydrocracking catalyst (s) at temperatures of 350-480 ° C, pressures of 20-400 bar, an LHSV of 2-20 1 / 1`h, and that the portion with boiling points> 350 ° C 20-70% reduced.

Die Altöle bzw. deren Gemische können je nach Art und Menge an Verunreinigungen bzw. Beimengungen gemäß dem Stand der Technik vorbehandelt werden.
Beispielhaft seien genannt:

  • die Entfernung leicht siedender Anteile durch Abdestillieren;
  • die Sedimentation von Feststoffen;
  • die Abscheidung von Wasser;
  • Trocknung;
  • die Verdünnung mit Verdünnungsmitteln und anschließende Abtrennung von ausgeschiedenem Wasser oder ausgefällten Feststoffen;
  • Filtrieren;
  • Zentrifugieren;
  • Behandeln mit Adsorbentien wie beispielsweise Bleicherde, Perlite, Zellulosematerialen, Adsorptionskohle, u.a.;
  • Dampfbehandlung;
  • Extraktion (Lösungsmittelraffination);
  • überkritische Extraktion;
  • Destillation im Vakuum, ggfs. Dünnschichtverdampfung.
  • chemische Vorbehandlungen, wie beispielsweise die Behandlung mit Diammonphosphatlösung;
  • die hydrierende raffinierende Vorbehandlung;
  • Behandlung mit Schwefelsäure;
  • Behandlung mit Laugen oder Kalk, u.a.
Depending on the type and amount of impurities or admixtures, the waste oils or their mixtures can be pretreated in accordance with the prior art.
Examples include:
  • the removal of low-boiling fractions by distillation;
  • sedimentation of solids;
  • the separation of water;
  • Drying;
  • dilution with diluents and subsequent separation of water or precipitated solids;
  • Filter;
  • Centrifuge;
  • Treatment with adsorbents such as bleaching earth, perlite, cellulose materials, adsorption carbon, among others;
  • Steam treatment;
  • Extraction (solvent refining);
  • supercritical extraction;
  • Distillation in a vacuum, possibly thin film evaporation.
  • chemical pretreatments, such as treatment with diammon phosphate solution;
  • the hydrogenating refining pretreatment;
  • Treatment with sulfuric acid;
  • Treatment with lye or lime, among others

Obgleich die Gewinnung von Schmierstoffen mit hohem Viskositätsindex durch Hydrocracken von Einsatzprodukten mit einem hohen Anteil an geradkettigen Paraffinen bekannt ist, (s. beispielsweise: V.I. Karzhev, E.M. Nikonorov, E.I. Silchenko, A.I. Dintses, T.M. Komissarova, E.P. Detusbeva, S.Z. Levinson, 9. Welterdölkongreß, Applied Science Publishers, 1975, Bd. 5, S. 191), wobei die geradkettigen Paraffine z.Teil gespalten und isomerisiert werden, so daß nach Entwachsung ein Schmierstoff entsteht, der praktisch völlig aus verzweigten Paraffinen besteht, war es überraschend, daß auch bei Einsatz verbrauchter Schmierstoff, die fast keine geradkettigen Paraffine enthalten, ebenfalls durch das erfindungsgemäße Verfahren
Schmierstoffe mit hohem Viskositätsindex gewonnen werden können. Eine weitere vorteilhafte Wirkung des erfindungsgemäßen Verfahrens ist der Abbau der in Altöl enthaltenen synthetischen Schmierstoffe, wie beipielsweise der Esterschmierstoffe, der Polyalkylenglykole, Siliconschmierstoffe, Schwefel enthaltender Schmierstoffe und sonstiger. Hierdurch wird ein besonders wertvolles Schmierölprodukt erhalten, das praktisch völlig aus Kohlenwasserstoffen besteht und sich außer für die Anwendung als Schmierstoff auch hervorragend für den Einsatz als Ethylenfeed eignet, wobei über 30 Gew.% Ethylen erhalten werden können. Zusätzlich können auch die erhaltenen Kohlenwasserstoffe im Benzin- und Mittelöl-Siedebereich als Ethylenfeed eingesetzt werden.Although it is known to obtain lubricants with a high viscosity index by hydrocracking feedstocks with a high proportion of straight-chain paraffins (see, for example: VI Karzhev, EM Nikonorov, EI Silchenko, AI Dintses, TM Komissarova, EP Detusbeva, SZ Levinson, 9. Welterdölkongreß, Applied Science Publishers, 1975, Vol. 5, p. 191), whereby the straight-chain paraffins are partly split and isomerized, so that after dewaxing a lubricant is formed which consists practically entirely of branched paraffins, it was surprising that also when using used lubricant that contains almost no straight-chain paraffins, also by the method according to the invention
Lubricants with a high viscosity index can be obtained. A further advantageous effect of the process according to the invention is the degradation of the synthetic lubricants contained in waste oil, such as the ester lubricants, the polyalkylene glycols, silicone lubricants, lubricants containing sulfur and others. In this way, a particularly valuable lubricating oil product is obtained which consists practically entirely of hydrocarbons and, in addition to being used as a lubricant, is also outstandingly suitable for use as an ethylene feed, with over 30% by weight of ethylene being obtainable. In addition, the hydrocarbons obtained in the gasoline and medium oil boiling range can also be used as ethylene feed.

Als Hydrocrack-Katalysatoren können sowohl zeolithische als auch amorphe Katalysatoren erfindungsgemäß eingesetzt werden, wie sie beispielsweise im Handel erhältlich sind. Die aktiven Hydrocrack-Komponenten können beipielsweise Ni/Mo, Ni/W, Co/Mo, Co/W oder deren Gemische sein, aber auch andere Metalle bzw. Metallverbindungen beipielsweise aus der V. - VIII. Nebengruppe des Periodensystems. Demgemäß sind im erfindungsgemäßen Verfahren beispielsweise alle dem Stand der Technik entsprechenden Hydrocrack-Katalysatoren geeignet.According to the invention, both zeolitic and amorphous catalysts, such as are commercially available, can be used as hydrocracking catalysts. The active hydrocracking components can be, for example, Ni / Mo, Ni / W, Co / Mo, Co / W or mixtures thereof, but also other metals or metal compounds, for example from sub-group VIII to VIII of the periodic table. Accordingly, in the method according to the invention, for example, all are state of the art suitable hydrocracking catalysts.

Erfindungsgemäß werden jedoch amorphe Hydrocrack-Katalysatoren bevorzugt, wobei diese entsprechend dem Stand der Technik beipielsweise Aluminiumsilikate, SiO₂, Al₂O₃, u.a. Oxide als Basis enthalten können.According to the invention, however, amorphous hydrocracking catalysts are preferred, which according to the prior art, for example, aluminum silicates, SiO₂, Al₂O₃, etc. May contain oxides as a base.

Es wurde überraschend gefunden, daß amorphe und kristalline, zeolithische Katalysatoren zwar bezüglich Ausbeute und Viskositätsindex vergleichbare Ergebnisse liefern, daß jedoch in Gegenwart von amorphen Katalysatoren praktisch keine Erhöhung des Pour Points erfolgt, während in Gegenwart von kristallinen, zeolithischen Katalysatoren starke Zunahmen des Pour Points zu beobachten sind, so daß bei Einsatz der Produkte als Schmieröl im letzteren Falle anschließend eine Entwachsung erforderlich ist.
Im Falle des Einsatzes der erfindungsgemäßen Produkte als Ethylenfeed ist der Pour Point von nur geringem Einfluß.It was surprisingly found that amorphous and crystalline, zeolitic catalysts yield comparable results in terms of yield and viscosity index, but that in the presence of amorphous catalysts there is practically no increase in the pour point, whereas in the presence of crystalline, zeolitic catalysts there is a sharp increase in the pour point are observed, so that when the products are used as lubricating oil in the latter case dewaxing is required.
If the products according to the invention are used as ethylene feed, the pour point has only a minor influence.

Auch handelsübliche Raffinationskatalysatoren können ggfs. unter schärferen Bedingungen als Spalt-Katalysatoren erfindungsgemäß eingesetzt werden.Commercially available refining catalysts can optionally also be used according to the invention under more stringent conditions than gap catalysts.

Im allgemeinen werden die Katalysatoren erfindungsgemäß als Festbettkatalysatoren eingesetzt, jedoch werden auch bei Anwendung des Fließbett- oder Wirbelbett-Verfahrens, die erfindungsgemäßen Ergebnisse erhalten.
Ebenso können Methoden angewendet werden, bei denen sich der Katalysator in Suspension befindet.In general, the catalysts are used according to the invention as fixed bed catalysts, but the results according to the invention are also obtained when using the fluidized bed or fluidized bed process.
Methods can also be used in which the catalyst is in suspension.

Das erfindungsgemäß hydrierend zu behandelnde Einsatzprodukt wird mit Wasserstoff, Wasserstoff enthaltenden Gasen, die beispielsweise zusätzlich N₂, CO₂, Kohlenwasserstoffe und andere Beimengungen enthalten können umgesetzt oder auch mit Wasserstoff übertragenden Lösungsmitteln gemischt bei Temperaturen von 350 bis 480°C, Drücken von 20 bis 400 bar und einer LHSV von 2 bis 20 l/h`l, wobei die Bedingungen in Abhängigkeit vom Einsatzprodukt so eingestellt werden, daß der Anteil im Einsatzöl mit Siedepunkt > 350°C um 20 bis 70 % verringert wird. Bevorzugt wird bei einer Temperatur von 400 bis 460°C, einem Druck von 100 bis 350 bar und einer LHSV von 4 - 12 l/h`l gearbeitet und der Anteil im Einsatzöl mit Siedepunkt > 350°C um 30 - 60 % verringert.The feed product to be treated according to the invention is reacted with hydrogen, hydrogen-containing gases, which may additionally contain, for example, N₂, CO₂, hydrocarbons and other admixtures or mixed with hydrogen-transferring solvents at temperatures from 350 to 480 ° C., pressures from 20 to 400 bar and an LHSV of 2 to 20 l / h`l, the conditions being set depending on the feed product so that the proportion in the feed oil with a boiling point> 350 ° C. is reduced by 20 to 70%. The process is preferably carried out at a temperature of 400 to 460 ° C, a pressure of 100 to 350 bar and an LHSV of 4 - 12 l / h`l and the proportion in the feed oil with a boiling point> 350 ° C is reduced by 30 - 60%.

Die Hydriertemperatur kann auch ein Temperaturprofil z.B. ein Sägezahnprofil sein.The hydrogenation temperature can also be a temperature profile e.g. be a sawtooth profile.

Der spaltenden hydrierenden Behandlung wird bevorzugt, insbesondere bei Einsatz kristalliner Zeolith-Katalysatoren, eine Raffinationsstufe vorgeschaltet. Üblicherweise entspricht das Katalysatorvolumen der Raffinationsstufe ungefähr dem der Hvdrocrackstufe. Es sind jedoch je nach Einsatzölzusammensetzung auch Änderungen der Volumenverhältnisse in weiten Grenzen möglich, wie beispielsweise von 5:1 bis 1:5. Als Raffinationskatalysatoren können handelsübliche Produkte eingesetzt werden. Ferner kann, wie bereits oben ausgeführt, eine Stufe zur Entfernung von Metallen vorgeschaltet sein.The splitting hydrogenating treatment is preferred, in particular when using crystalline zeolite catalysts, before a refining step. The catalyst volume of the refining stage usually corresponds approximately to that of the hydrocracking stage. However, depending on the composition of the feed oil, changes in the volume ratios are possible within wide limits, for example from 5: 1 to 1: 5. Commercial products can be used as refining catalysts. Furthermore, as already explained above, a stage for removing metals can be installed.

Erfindungsgemäß kann auch ein Katalysator eingesetzt werden, der sowohl raffinierend als auch spaltend wirkt, wobei bevorzugt zwei getrennte Katalysatorbetten verwendet werden, die unter unterschiedlichen Bedingungen betrieben werden, insbesondere bei höherer Temperatur in der Krackstufe.According to the invention, it is also possible to use a catalyst which has both refining and cleavage properties, preferably two separate catalyst beds which are operated under different conditions, in particular at a higher temperature in the cracking stage.

Überraschend wurde gefunden, daß nach dem erfindungsgemäßen Verfahren bei Einsatz von Altölen Schmieröle erhalten werden, die frei sind von Sauerstoff, Halogen, Stickstoff, Schwefel und Metallen und Viskositätsindexwerte (VI) von 110 bis 130 besitzen, wobei gute bis hohe Ausbeuten in Abhängigkeit vom Viskositätsindex erhalten werden.
Die Einsatz-Altöle können auch beispielsweise synthetische Öle auf Polyether-, Polyglykol-, Polyesterbasis, Polychlorbiphenyle , u.a. enthalten oder kleine Anteile an Ölen mit Viskositätsindex < 90, wie beispielsweise Transformatorenöle. Ggfs. können auch Rohölanteile, Rückstandsölanteile mineralischen oder Kohleursprungs sowie ähnliche Öle beigemischt sein, wie beispielsweise aus Ölschiefer, Ölsanden und dergleichen, wobei ggfs. eine Entwachsung nachgeschaltet wird.Surprisingly, it was found that the process according to the invention uses waste oils Lubricating oils are obtained which are free from oxygen, halogen, nitrogen, sulfur and metals and have viscosity index values (VI) of 110 to 130, good to high yields being obtained depending on the viscosity index.
The used waste oils can also contain, for example, synthetic oils based on polyether, polyglycol, polyester, polychlorobiphenyls, etc. or small proportions of oils with a viscosity index <90, such as transformer oils. If necessary. can also be mixed with crude oil, residual oil from mineral or coal origins and similar oils, such as from oil shale, oil sands and the like, with dewaxing being added if necessary.

Durch das erfindungsgemäße Verfahren lassen sich aus den genannten Ölen ca.25-75 % HVI-Öle (HVI = Hoher Viskositäts-Index) gewinnen, neben niedriger siedenden Produkten, vor allem solchen aus dem Mittelöl- und Benzinbereich.Using the process according to the invention, about 25-75% HVI oils (HVI = high viscosity index) can be obtained from the oils mentioned, in addition to lower-boiling products, especially those from the middle oil and petrol sectors.

Die erfindungsgemäßen Bedingungen führen zusätzlich zum nahezu vollständigen Abbau der Verbindungen mit Heteroelementen im Einsatzprodukt. So sind chlorhaltige Verbindungen im Schmiermittelprodukt nicht mehr nachweisbar, ebenso werden Schwefel- und Stickstoffverbindungen, die beipielsweise aus den beigefügten gelösten Additiven stammen, nahezu vollständig abgebaut.The conditions according to the invention additionally lead to the almost complete degradation of the compounds with hetero elements in the feed product. For example, chlorine-containing compounds are no longer detectable in the lubricant product, and sulfur and nitrogen compounds, which for example derive from the added dissolved additives, are almost completely broken down.

Die unter den erfindungsgemäßen Bedingungen erhaltenen Produkte eignen sich auch hervorragend als Feed zum Einsatz in Ethylenanlagen. Hierbei ist wie im Falle der Herstellung von Schmiermitteln mit hohem Viskositätsindex zu beachten, daß in Abhängigkeit vom eingesetzten Altöl bzw. Altölgemisch, Temperatur, Druck und Verweilzeit entsprechend anzupassen sind.The products obtained under the conditions according to the invention are also outstandingly suitable as feeds for use in ethylene plants. Here, as in the case of the production of lubricants with a high viscosity index, it should be noted that, depending on the used oil or used oil mixture, temperature, pressure and residence time have to be adjusted accordingly.

Die Erfindung wird anhand der folgenden Beipiele näher erläutert.The invention is illustrated by the following examples.

Beipiel 1Example 1

Technisches, vorgereinigtes Altöl wurde einer Vakuumdestillation unterworfen unter technisch üblichen Bedingungen. Der Siedeschnitt mit der ASTM D 1160-Siedeanalyse:

10 % bis 392°C
50 % bis 462°C
90 % bis 471°C
Viskositätsindex 102

der 4,5 Gew.% eines synthetischen Esteröls enthielt, wurde bei einer LHSV von 8 l/l h, einem Druck von 220 bar bei 410°C in Gegenwart eines amorphen handelsüblichen Hydrocrack-Katalysators hydrierend gespalten. Es wurden 30 % des > 350°C siedenden Anteils abgebaut.
Es wurden 60 % bezogen auf das Einsatzprodukt, an Esteröl freiem Schmieröl mit einem Viskositätsindex von 115 erhalten mit einem Siedebereich > 400°C. Zusätzlich wurden tiefer siedende Produkte, vor allem im Mittelöl- und Benzinbereich erhalten.Technical, pre-cleaned waste oil was subjected to a vacuum distillation under the usual technical conditions. The boiling cut with the ASTM D 1160 boiling analysis:

10% to 392 ° C
50% to 462 ° C
90% to 471 ° C
Viscosity index 102

which contained 4.5% by weight of a synthetic ester oil was hydrogenated at an LHSV of 8 l / lh, a pressure of 220 bar at 410 ° C. in the presence of an amorphous commercial hydrocracking catalyst. 30% of the> 350 ° C boiling portion was broken down.
60%, based on the starting product, of lubricating oil free of ester oil and having a viscosity index of 115 and a boiling range> 400 ° C. were obtained. In addition, lower-boiling products were obtained, especially in the middle oil and petrol sector.

Beispiel 2Example 2

Der Versuch gemäß Beispiel 1 wurde wiederholt, es wurde jedoch bei 440°C gearbeitet und der > 350°C siedende Anteil zu 60 % abgebaut.
Es wurden 30 % eines Esteröl freien Schmieröls erhalten mit einem Viskositätsindex von 125 und einem Siedebereich >400°C. Ähnliche Ergebnisse wurden bei Vorschaltung unterschiedlicher Raffinationen erhalten.The experiment according to Example 1 was repeated, but the process was carried out at 440 ° C. and the portion boiling> 350 ° C. was reduced to 60%.
30% of an ester oil-free lubricating oil were obtained with a viscosity index of 125 and a boiling range> 400 ° C. Similar results were obtained with different refining upstream.

Beipiel 3Example 3

Die Versuche gemäß den Beipielen 1 und 2 wurden wiederholt, jedoch in Gegenwart eines kristallinen, zeolithischen, handelsüblichen Hydrocrack-Katalysators. Es wurden nahezu die gleichen Ergebnisse erhalten wie in den Beispielen 1 und 2.The experiments according to Examples 1 and 2 were repeated, but in the presence of a crystalline, zeolitic, commercially available hydrocracking catalyst. Almost the same results were obtained as in Examples 1 and 2.

Beipiel 4Example 4

Die gemäß Beispiel 1 und 2 erhaltenen Schnitte >400°C wurden hinsichtlich ihres Pour Point untersucht. Es wurden folgende Ergebnisse erhalten:

Figure imgb0001
The sections> 400 ° C. obtained according to Examples 1 and 2 were examined with regard to their pour point. The following results were obtained:
Figure imgb0001

Beipiel 5Example 5

Vorgereinigtes und destilliertes Altöl mit einem Anteil von 3 Gew.% Polyalkylenglykol-Schmieröl wurde unter Abbau des > 350°C siedenden Anteils um 20 % über einem amorphen Katalysator hydrierend umgesetzt.
Es wurden 73 % eines > 400°C siedenden Polyalkylenglykolfreien Schmieröls mit einem Viskositätsindex von 110 erhalten.Pre-cleaned and distilled waste oil with a proportion of 3% by weight of polyalkylene glycol lubricating oil was reacted with a 20% degradation over a boiling portion> 350 ° C. over an amorphous catalyst.
73% of a> 400 ° C. boiling polyalkylene glycol-free lubricating oil with a viscosity index of 110 were obtained.

Beispiel 6Example 6

Vorgereinigtes und destilliertes Altöl mit einem Anteil von 7 Gew.% an polare Gruppen enthaltenden synthetischen Schmierstoffen wurde unter Abbau des > 350°C siedenden Anteils um 70 % über einem amorphen Katalysator hydrierend umgesetzt. Es wurden 21 % eines > 400°C siedenden Schmieröls, das frei von polaren Gruppen war , mit einem Viskositätsindex von 129 erhaltenPre-cleaned and distilled waste oil with a proportion of 7% by weight of synthetic lubricants containing polar groups was reacted with a 70% degradation of the> 350 ° C. boiling proportion over an amorphous catalyst. 21% of a> 400 ° C. boiling lubricating oil which was free of polar groups and had a viscosity index of 129 was obtained

Beispiel 7Example 7

Beispiel 5 wurde wiederholt, wobei das Einsatzöl 6000 ppm Polychlorbiphenyl (PCB) enthielt.
Im Produkt wurden < 1 ppm PCB gefunden.Example 5 was repeated, the feed oil containing 6000 ppm polychlorobiphenyl (PCB).
<1 ppm PCB was found in the product.

Ähnlich gute Ergebnisse wurden auch erhalten bei in Abhängigkeit vom Altöl unterschiedlichen Temperaturen, Drücken und Verweilzeiten.Similar good results were also obtained with different temperatures, pressures and residence times depending on the waste oil.

Ähnlich gute Ergebnisse werden ferner erfingungsgemäß erhalten, wenn eine andere Vorreinigung das Einsatz-Altöl erfolgt als der Vakuumdestillation.According to the invention, similarly good results are also obtained if the used waste oil is pre-cleaned differently than vacuum distillation.

Die Vorreinigung ist so zu wählen, daß der Katalysator durch Verunreinigungen nicht geschädigt bzw. nur wenig geschädigt wird bzw. wenig inaktiviert wird. Es sind daher in Abhängigkeit vom eingesetzten Altöl aus dem Stand der Technik die geeigneten Maßnahmen zu ergreifen.The pre-cleaning should be selected so that the catalyst is not damaged or only slightly damaged or is inactivated little by impurities. Suitable measures must therefore be taken depending on the used oil from the state of the art.

Claims (2)

  1. Process for producing high-quality lubricants from waste oils by catalytic hydrogenation of waste oils or mixtures thereof with hydrogen and/or hydrogen-containing gases and/or hydrogen-transferring solvents, optionally freed from solid material, other dissolved and/or emulsified additives and water and,optionally, pretreated chemically and/or physically, characterized by carrying out the hydrogenating treatment in the presence of one or more commercial hydrocracking catalyst(s) at temperatures of 350-480 °C, pressures of 20-400 bar and a LHSV of 2-20 1/1 x h and reducing that portion having a boiling point of greater than 350 °C by 20-70 %.
  2. Process according to claim 1 characterized by using as a hydrocracking catalyst an amorphous catalyst and carrying out the hydrogenating treatment at a temperature of 400-460 °C, a pressure of 100-350 bar and a LHSV of 4-12 1/1 x h and reducing that portion having a boiling point of greater than 350°C.
EP86117551A 1986-01-02 1986-12-17 Process for obtaining high-grade lubricants from spent oils Expired - Lifetime EP0228651B1 (en)

Priority Applications (1)

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AT86117551T ATE62928T1 (en) 1986-01-02 1986-12-17 PROCESS FOR RECOVERING HIGH-QUALITY LUBRICANTS FROM WASTE OILS.

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DE3600024A DE3600024C1 (en) 1986-01-02 1986-01-02 Process for extracting high quality lubricants from altoeles
DE3600024 1986-01-02

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EP0228651B1 true EP0228651B1 (en) 1991-04-24

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DE3723607A1 (en) * 1987-07-17 1989-01-26 Ruhrkohle Ag METHOD FOR HYDROGENATING WORKOUT OF ALTOELS
ES2020603B3 (en) * 1987-07-23 1991-08-16 Uop (A New York General Partnership) TREATMENT OF A TEMPERATURE SENSITIVE HYDROCARBONACEOUS EFFLUENT CONTAINING A NON-DISTILLABLE COMPONENT
DE3839799A1 (en) * 1988-11-25 1990-07-05 Rwe Entsorgung Ag METHOD FOR PROCESSING CONTAMINATED OILS
DE102006057910A1 (en) * 2006-12-08 2008-07-03 Exad Gmbh Treatment of used oil, water and oil mixtures, or solvent and water mixtures, first extracts impurities, then exposes to regenerable adsorbent material
FI128237B (en) * 2018-12-21 2020-01-15 Neste Oyj Method for upgrading waste oil

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US3980551A (en) * 1975-12-18 1976-09-14 Hydrocarbon Research, Inc. Refining of waste lube oil to prepare usable lubestock

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