EP0377606B1 - Process for purifying and regenerating used oils - Google Patents

Process for purifying and regenerating used oils Download PDF

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Publication number
EP0377606B1
EP0377606B1 EP88907226A EP88907226A EP0377606B1 EP 0377606 B1 EP0377606 B1 EP 0377606B1 EP 88907226 A EP88907226 A EP 88907226A EP 88907226 A EP88907226 A EP 88907226A EP 0377606 B1 EP0377606 B1 EP 0377606B1
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Prior art keywords
oil phase
temperature
oil
pretreated
solution
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German (de)
French (fr)
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EP0377606A1 (en
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Adekunle Onabajo
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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
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • the invention relates to a process for cleaning and regenerating used oils, in particular used lubricating oils, by filtration, heat treatment and stripping off the low boilers consisting of solvent and water.
  • Waste oils are used mineral oils, especially used engine and lubricating oils.
  • the utility value of mineral lubricating oils is greatly affected by oxidation products, pollution and other additives that accumulate during use. Such products no longer fully fulfill their task and must be replaced. They are referred to as waste oils and are collected and processed for reasons of environmental protection, raw material conservation and also from an economic point of view.
  • Waste oils mainly consist of a base oil based on mineral oil or synthetic oil, but contain considerable amounts of foreign substances, e.g. As water, solvents, fuels, asphalt-like substances, acids, resins, ashes and additives such as antioxidants, anti-corrosion agents, wetting agents, dispersants, anti-foaming agents and viscosity index improvers.
  • the additives can contain halogen, sulfur and nitrogen compounds and numerous other, partly toxic components.
  • Waste oils are first cleaned mechanically by separating undissolved impurities and foreign substances by sedimentation, filtration or centrifugation. The separation can be accelerated considerably by heating the used oil to 50 to 100 ° C.
  • Waste oil is subjected to a refining hydrogenation over nickel-molybdenum catalysts after pretreatment with an aqueous diammonium phosphate solution.
  • polychlorinated biphenyls are also said to be at least partially degraded in this process, chlorinated solvents and cleaning liquids, metalworking oils and other processing oils and their composition are intended for the regeneration of this process is not clearly identified, and insulating and transformer oils have not been preserved in the feed. Suitable starting products for this process are therefore essentially used engine oils.
  • the waste oil is freed of water and dirt by sedimentation and residual water and low boilers by atmospheric distillation.
  • the gas oil fraction is then separated off in a separate stage.
  • the lubricating oil components are fractionated, condensed and dirt, additives and some of the oxidation products are removed as sump.
  • the distillates are hydrofinished and stripped. Since acid refining is also absent in this process, additives or foreign components must either be separable by distillation or convertible by hydrogenation. Ingredients must not affect the activity of the hydrogenation catalyst, so that, for. B. Cutting oils with contents of halogenated hydrocarbons cannot be processed by this method either, see Ullmanns Encyklopadie der Technische Chemie, 4th edition volume 20, page 500.
  • the oxidation products and additives are also not removed with sulfuric acid, but by treatment with finely dispersed sodium, whereby they either polymerize or are converted into sodium salts which have a boiling point so high that the oil is distilled can.
  • the distillation takes place in two steps, the second of which is designed as a short-path thin-film evaporation for separating the reaction products.
  • the invention has for its object to develop a universally applicable method that allows pollutants and other undesirable components from used lubricating oils and other waste oils with higher product yields and higher product quality with less process effort and in particular less landfill than what is possible according to the prior art remove.
  • the process is said to be particularly suitable for special treatments, the hydrogenation or, for example, the treatment with sodium and to bring about simplifications in terms of process technology and the associated cost reductions, for example by avoiding catalyst poisoning when the hydrogenation stage is switched on.
  • process stage (2) dewatering takes place in particular.
  • the feed materials bind the water as residue sludge, which is then separated in a known manner by separation. 50 to 80% of the free water present in the waste oil is separated in this way.
  • the residual water and the low boilers are then removed by distillation in process step (3).
  • the waste oil treatment according to process steps (1) to (3) takes place in a temperature range from 50 to 140 ° C, with temperatures as low as possible being preferred in this range.
  • PCB accumulation in the low boilers and water is excluded, since the boiling point range of polychlorinated bi- and terphenylene is above the stripping temperature. PCB separation therefore does not take place in process stage (3), which ensures that the low boilers and water obtained by this process are not contaminated with PCB. This is of great importance for an environmentally friendly process for waste oil processing.
  • Process stage 3 can also be carried out before process stage 2 by first separating the low boilers from the mixture obtained, then letting them settle in a decanter and finally separating the sedimented material.
  • the alkali water glass solutions and / or the polyalkylene glycol solutions are preferably preheated, in particular to 30 to 60 ° C., preferably to about 50 ° C.
  • An alternative method of operation is to heat in process stage (1) to a temperature of 60 to 80 ° C. in a closed agitator and, with intensive stirring, to add 0.5 to 2.5% by weight, based on the waste oil.
  • a hydrogenation treatment step known per se can be switched between process step (3) and process step (4), in which, in the presence of a hydrogenation-active catalyst, in particular at 200 to 400 ° C. and 10 to 200 105 Pa (10 to 200 bar ) and preferably at 300 to 380 ° C and 40 to 60 105 Pa (40 to 60 bar) the pretreated oil phase is hydrogenated.
  • a hydrogenation-active catalyst in particular at 200 to 400 ° C. and 10 to 200 105 Pa (10 to 200 bar ) and preferably at 300 to 380 ° C and 40 to 60 105 Pa (40 to 60 bar) the pretreated oil phase is hydrogenated.
  • the filter insert of process stage (4) or (8) is regenerated if necessary by washing it free of the adsorbed material with a solvent.
  • a ketone solvent is preferably used for this purpose, which in particular consists of one or more solvents each having a boiling point of 50 to 80 ° C. and is in particular acetone or methyl ethyl ketone.
  • the treated oil phase is finally subjected to vacuum distillation at a temperature of 200 to 300 ° C. and a pressure of 0.13 kPa to 6.67 kPa (1 to 50 torr).
  • a further embodiment of the process according to the invention provides for treatment of the dry oil phase (with water contents ⁇ 0.1% by weight) in a manner known per se after process step (3). with finely dispersed sodium.
  • Process steps (1) to (3) are able to deliver a constant water-free oil flow, which is the most important requirement for the use of sodium. Since the oxidation products and the non-PCB chlorine compounds are largely removed by the pretreatment in this water-free oil stream, the sodium process is economically viable.
  • the sodium required for the waste oil treatment is added to the pretreated waste oil in the form of a dispersion, in particular consisting of sodium particles of 5 to 10 ⁇ m, in a base oil of a similar composition to motor oils.
  • a dispersion in particular consisting of sodium particles of 5 to 10 ⁇ m, in a base oil of a similar composition to motor oils.
  • sodium in an oil, preferably reraffinate is melted and finely divided in a disperser, so that particle sizes of ⁇ 20 ⁇ m are achieved.
  • a dispersion of 33% by weight sodium is particularly suitable for the treatment of the pretreated dry oil stream.
  • the amount of dispersion added is matched to the content of inorganic chlorine.
  • the treatment temperature and time depend on the quality of the drying oil. Normally, a temperature range from 20 ° C to 250 ° C and especially in a temperature range from 100 to 200 ° C and in a period of 1 to 30 minutes reliable PCB separation can be achieved.
  • the base oil obtained is characterized by a cheaper and higher viscosity index than fresh oil. All ash-forming additives - otherwise the cause of sludge formation are removed, i.e. H. the ash content is practically 0% by weight. The viscosity improvement additives are largely retained, namely at least 1/3 of the corresponding additives in the fresh additive package.
  • Contaminants in waste oil form stable dispersions due to the presence of detergents. Additives prevent the physical separation of the contaminants by gravity and / or centrifugal force.
  • the flocculation and adsorbents namely alkali water glass and polyalkylene glycol of the formula given, destabilize the dispersion in process step (1). The differences in density between the oil and foreign matter phases are effective.
  • the chlorine compounds are chemically converted and NaCl and non-chlorinated compounds are formed. The oxidation products are neutralized and the converted and neutralized products are adsorbed.
  • process stage (2) impurities and the flocculants and adsorbents are separated off.
  • the flocculated, dispersed impurities are eliminated by decanters or separators as a result of the destabilization which took place in stage (1) and the density differences which became effective in stage (1) by the action of gravity or minimal centrifugal forces.
  • process stage (3) the low boilers, namely polar and non-polar solvents, and water are removed.
  • the solvent and adsorbent additive in process step (6) is used for the further precipitation of finely dispersed impurities, here these additives bring about the removal of polychlorinated bi- and terphenylene and the solvent additive supports the subsequent filtering adsorption step. If there are no polychlorinated bi- and terphenyls, the addition of the n-alkanes can be used to go directly to the filtering adsorption stage without the further addition of adsorbents - see process stage (4).
  • Process stage (6) with the addition of solvent and adsorbent is followed by process stage (7), which largely corresponds to process stage (2).
  • the filtering adsorption takes place in process stage (8) or (4). In this stage, the remaining dissolved and undissolved impurities and unwanted residual additives are specifically bound to the adsorbents.
  • the lubricating oil components (hydrocarbons) pass through the adsorbents.
  • This filtering adsorption is a multi-parameter separation method, which is characterized in that two chemically different substances or two chemically different groups of substances are separated from one another due to their different adsorption capacity, by allowing a specific solvent and an adsorbent to act on the mixture.
  • the filtering adsorption differs in that there is only a single phase during the separation, while the filtration requires two phases, generally solid / liquid.
  • the filtering adsorption distinguished by its selectivity, which is achieved by the selective solvent and a selected adsorbent, here bleaching earth or compacted aluminum oxide, see "Filtering adsorption", W. Fuchs, F. Glaser and E. Bendel, chemistry Engineering technology 1959, pages 677 679.
  • Adsorbed material namely 5 to 10% by weight of finely dispersed, dissolved oxidation products and residual additives, are desorbed with suitable solvents, solvents with a boiling point of up to 80 ° C., in particular acetone or methyl ethyl ketone.
  • the adsorbent is dried at about 60 to about 120 ° C., preferably about 100 ° C., under a protective gas, preferably nitrogen, and then brought to the temperature required for process step (8).
  • the adsorbent is now ready for use again and can be used continuously at these values.
  • the lubricating oil constituents (about 1.5% by weight) which are contained in the adsorbent are dissolved out before the adsorbent regeneration (with acetone or methyl ethyl ketone) by solvent rinsing, in particular with n-heptane, and fed to process stage (6) or (9).
  • This step serves to increase the yield of the regrind.
  • the residual additives and oxidation products obtained after evaporation of the solvent are used as additives, for example for asphalt processing.
  • PCBs, chlorinated dioxins, furans and aliphates with chlorine contents> 5% can be broken down below the detection limit in this way.
  • the recovered solvent is used again for solvent rinsing.
  • step (5) or (9) the solvent is separated from the regenerate and returned in step (4) or (6).
  • the final oil phase is a mixture of lubricating oil fractions with different flash points and viscosities, the fractions must be separated under vacuum and temperatures above 200 ° C.
  • the swamp is base oil.
  • the process comprising process steps (1) to (3) can be used for decentralized waste oil processing, in that the collected waste oils are brought together in area collection points and treated in decentralized small plants according to the process comprising process steps (1) to (3) as a partial process.
  • the waste oil treated in this way can then be subjected to the process according to one or more of the subclaims, in particular for the removal of chlorine compounds and perchlorinated bi- and terphenylene, in a central large-scale plant.
  • Adsorbent regeneration with acetone, methyl ethyl ketone (technical).
  • Filters used stainless steel, sieve mesh 20 ⁇ m to 200 ⁇ m; Glass fiber filter and non-woven filter.
  • the mixture obtained was sedimented in a decanter at 70 ° C with a throughput of 3,000 ml / h and the oil phase separated.
  • the low boilers and the residual water were separated from the oil phase at a temperature of 130 ° C. and a pressure of 6.67 kPa (50 torr).
  • Waste oil not containing PCBs was treated with n-heptane in the ratio of oil phase to n-heptane of 1: 4 parts by weight as a dry oil phase pretreated according to Example 1 in a closed agitator, and stirred intensively at 40 ° C. for 30 minutes.
  • the oil solution was then sedimented in a decanter at 10 to 20 ° C. with a throughput of 12,000 ml / h, and then the oil solution was separated from the precipitation residue.
  • PCB-containing waste oil was mixed in a closed agitator after the addition of n-heptane in the ratio oil phase to n-heptane of 1: 4 parts by weight to the oil phase pretreated according to Example 1 with intensive stirring at 80 ° C with a mixture of 0 preheated to 50 ° C , 25% by weight soda water glass 50/51 (alkaline) and 0.1% by weight of polyethylene glycol (average molecular weight 600, OH number 170 mgKOH / g), each based on the dry oil phase.
  • the mixture was stirred vigorously at 70 ° C. for about 110 minutes.
  • 0.1% by weight of anhydrous sodium metasilicate was added and the mixture was stirred for a further 10 minutes.
  • the oil solution was sedimented in a decanter at 10 to 20 ° C with a throughput of 12,000 ml / h and the oil solution was separated from the residue.
  • the oil solution from Examples 2 and 3 was subjected to a "filtering adsorption".
  • the adsorber consisted of a stainless steel screen mesh (20 - 40 ⁇ m) and an adsorbent pack with bleaching earth, Tonsil CCG 30/60.
  • the undesired oil components were adsorbed at 40 ° C. It was regenerated with n-heptane.
  • the throughput of regenerated solution was 3,000 ml / h.
  • the solvent n-heptane was recovered from the regenerated solution by distillation at 70 ° C. and a pressure of 6.67 kPa (50 torr).
  • the regenerate obtained was a mixture of lubricating oil fractions with different flash points and viscosities.
  • the fractions were separated under vacuum at 250-300 ° C and a pressure of before 0.13 kPa to 1.3 kPa (1 to 10 Torr).
  • the base oil was obtained as the sump.
  • the adsorber has been regenerated by desorbing the adsorbed impurities (oxidation products, unwanted residual additives, degradation products, etc.) at 50 ° C with acetone (boiling point 56 ° C).
  • the adsorber was dried under a stream of nitrogen at 60 ° C. and made reusable.
  • the resulting acetone solution was subjected to distillation to remove acetone from the waste.
  • the acetone was used again.
  • the wastes from Examples 1, 2, 3 and 4 were used as additives in the concentration range 0.5 to 5% by weight (based on bitumen) for asphalt modification.
  • process stage (4) instead of process stage (4) or (8), thin-film evaporation known per se can be carried out. Likewise, following the treatment with dispersed sodium, the oil phase obtained can be subjected to thin-film evaporation instead of process step (4).
  • the base oil obtained was characterized by a cheaper and higher viscosity index than the fresh oil. All ash-forming additives - otherwise causing sludge formation (especially in the engine) - are removed, ie the base oil obtained has an ash content of almost 0.0% by weight. Finally, the additives to improve the viscosity are largely retained, in accordance with previous ones Results at least about a third of the content of the fresh additive package in these additives.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Used oils, in particular spent lubricating oils, are coarse filtered and then mixed with an aqueous solution of sodium or potassium silicate and an aqueous solution of polyalkylene glycol at high temperature with stirring. The mixture obtained is allowed to stand, the sediment is separated, and water and light volatiles are separated from the oil phase by distillation. The dried oil phase obtained can be subjected, either directly or by a known treatment with dispersed sodium, to filtration adsorption and then fractionally distilled.

Description

Die Erfindung betrifft ein Verfahren zur Reinigung und Regenerierung von Altölen, insbesondere von gebrauchten Schmierölen, durch Filtrierung, Wärmebehandlung und Abstreifen der aus Lösungsmittel und Wasser bestehenden Leichtsieder.The invention relates to a process for cleaning and regenerating used oils, in particular used lubricating oils, by filtration, heat treatment and stripping off the low boilers consisting of solvent and water.

Altöle sind gebrauchte Mineralöle, insbesondere gebrauchte Motoren- und Schmieröle. Der Gebrauchswert von Mineralschmierölen wird durch Oxydationsprodukte, Verschmutzung und sonstige Beimengungen, die sich während der Anwendung ansammeln, stark beeinträchtigt. Derartige Produkte werden ihrer Aufgabe nicht mehr voll gerecht und müssen ausgetauscht werden. Sie werden als Altöle bezeichnet und aus Gründen des Umweltschutzes, der Rohstoffkonservierung und auch aus wirtschaftlichen Gesichtspunkten gesammelt und aufgearbeitet. Altöle bestehen überwiegend aus einem Grundöl auf Mineralöl- oder Syntheseölbasis, enthalten jedoch erhebliche Fremdstoffanteile, z. B. Wasser, Lösungsmittel, Kraftstoffe, asphaltartige Stoffe, Säuren, Harze, Aschen und Additive wie Antioxydantien, Korrosionsschutzmittel, Netzmittel, Dispergiermittel, Schaumverhütungsmittel und Viskositätsindexverbesserer. Die Additive können Halogen-, Schwefel- und Stickstoffverbindungen und zahlreiche andere, zum Teil toxische Komponenten enthalten.Waste oils are used mineral oils, especially used engine and lubricating oils. The utility value of mineral lubricating oils is greatly affected by oxidation products, pollution and other additives that accumulate during use. Such products no longer fully fulfill their task and must be replaced. They are referred to as waste oils and are collected and processed for reasons of environmental protection, raw material conservation and also from an economic point of view. Waste oils mainly consist of a base oil based on mineral oil or synthetic oil, but contain considerable amounts of foreign substances, e.g. As water, solvents, fuels, asphalt-like substances, acids, resins, ashes and additives such as antioxidants, anti-corrosion agents, wetting agents, dispersants, anti-foaming agents and viscosity index improvers. The additives can contain halogen, sulfur and nitrogen compounds and numerous other, partly toxic components.

Altöle werden zunächst mechanisch gereinigt, indem ungelöste Verunreinigungen und Fremdstoffe durch Sedimentation, Filtration oder Zentrifugieren abgetrennt werden. Die Abtrennung kann durch Erwärmen des Altöls auf 50 bis 100 °C erheblich beschleunigt werden.Waste oils are first cleaned mechanically by separating undissolved impurities and foreign substances by sedimentation, filtration or centrifugation. The separation can be accelerated considerably by heating the used oil to 50 to 100 ° C.

Die konventionelle Regeneration von Altölen erfolgt in einem mehrstufigen Prozeß, wie er in Ullmanns Encyklopädie der technischen Chemie 4. Auflage, Band 20 Seite 498 beschrieben ist. Nach der Grobentfernung von Wasser und festen Fremdstoffen werden durch atmosphärische Destillation bei etwa 250 °C leichtsiedende Anteile und Restwasser entfernt, sodann durch Schwefelsäureraffination mit anschließender Kalkneutralisation Oxydationsprodukte und Additive entfernt und der Raffinationsschlamm durch Dekantieren bzw. Filtrieren abgetrennt. Die Aufteilung in ein bis zwei Leicht- bzw. Mittelviskosedestillat- und Rückstandsfraktionen erfolgt durch Vakuumdestillation bei 80 bis 100 mbar, und schließlich werden die Fraktionen durch Bleicherdebehandlung aufgehellt und stabilisiert.The conventional regeneration of waste oils takes place in a multi-stage process, as described in Ullmann's Encyclopedia of Industrial Chemistry 4th Edition, Volume 20, page 498. After the rough removal of water and solid foreign substances, low-boiling fractions and residual water are removed by atmospheric distillation at about 250 ° C., then oxidation products and additives are removed by sulfuric acid refinement with subsequent lime neutralization, and the refining sludge is separated off by decanting or filtering. The division into one or two light or medium-viscosity distillate and residue fractions is carried out by vacuum distillation at 80 to 100 mbar, and finally the fractions are lightened and stabilized by bleaching earth treatment.

Nach dem PROP-Verfahren der Phillips Petroleum Co., wie es in Hydrocarbon Processing, September 1979,Seiten 148 ff. beschrieben ist, wird Altöl nach einer Vorbehandlung mit einer wäßrigen Diammoniumphosphatlösung einer raffinierenden Hydrierung über Nickel-Molybdän-Katalysatoren unterworfen. Obwohl bei diesem Verfahren angeblich auch polychlorierte Biphenyle zumindest teilweise abgebaut werden , sollen für dieses Verfahren der Regenerierung chlorierte Lösungsmittel und Reinigungsflüssigkeiten, Metallbearbeitungsöle sowie andere Bearbeitungsöle, deren Zusammensetzung nicht klar identifiziert ist, sowie Isolier- und Transformatorenöle im Einsatzmaterial nicht erhalten sein. Geeignete Einsatzprodukte für dieses Verfahren sind daher im wesentlichen Alt-Motorenöle.According to the PROP process from Phillips Petroleum Co., as described in Hydrocarbon Processing, September 1979, pages 148 ff., Waste oil is subjected to a refining hydrogenation over nickel-molybdenum catalysts after pretreatment with an aqueous diammonium phosphate solution. Although polychlorinated biphenyls are also said to be at least partially degraded in this process, chlorinated solvents and cleaning liquids, metalworking oils and other processing oils and their composition are intended for the regeneration of this process is not clearly identified, and insulating and transformer oils have not been preserved in the feed. Suitable starting products for this process are therefore essentially used engine oils.

Nach dem KTI-Verfahren der Kinetics Technology International wird das Altöl durch Sedimentation von Wasser und Schmutz und durch atmosphärische Destillation von Restwasser und Leichtsiedern befreit. Sodann wird in einer separaten Stufe die Gasölfraktion abgetrennt. In der folgenden Vakuumdestillation werden die Schmierölanteile fraktioniert, kondensiert und Schmutz, Additive und ein Teil der Oxydationsprodukte als Sumpf abgezogen. Die Destillate werden hydrofiniert und gestrippt. Da auch bei diesem Verfahren die Säureraffination fehlt, müssen Additive bzw. Fremdkomponenten entweder durch Destillation abtrennbar oder durch Hydrierung umwandelbar sein. Inhaltsstoffe dürfen die Aktivität des Hydrierkatalysators nicht beeinträchtigen, so daß z. B. Schneidöle mit Gehalten an halogenen Kohlenwasserstoffen nach diesem Verfahren ebenfalls nicht verarbeitet werden können, siehe Ullmanns Encyklopädie der technischen Chemie, 4. Auflage Band 20, Seite 500.According to the KTI process from Kinetics Technology International, the waste oil is freed of water and dirt by sedimentation and residual water and low boilers by atmospheric distillation. The gas oil fraction is then separated off in a separate stage. In the following vacuum distillation, the lubricating oil components are fractionated, condensed and dirt, additives and some of the oxidation products are removed as sump. The distillates are hydrofinished and stripped. Since acid refining is also absent in this process, additives or foreign components must either be separable by distillation or convertible by hydrogenation. Ingredients must not affect the activity of the hydrogenation catalyst, so that, for. B. Cutting oils with contents of halogenated hydrocarbons cannot be processed by this method either, see Ullmanns Encyklopadie der Technische Chemie, 4th edition volume 20, page 500.

Bei den Recyclon-Verfahren werden die Oxydationsprodukte und Additive ebenfalls nicht mit Schwefelsäure, sondern durch eine Behandlung mit fein dispergiertem Natrium entfernt, wodurch sie entweder polymerisieren oder in Natriumsalze übergeführt werden, die einen so hohen Siedepunkt haben, daß das Öl destilliert werden kann. Die Destillation erfolgt in zwei Schritten, von denen der zweite als Kurzweg-Dünnschicht-Verdampfung zur Abtrennung der Reaktionsprodukte ausgebildet ist.In the recycling process, the oxidation products and additives are also not removed with sulfuric acid, but by treatment with finely dispersed sodium, whereby they either polymerize or are converted into sodium salts which have a boiling point so high that the oil is distilled can. The distillation takes place in two steps, the second of which is designed as a short-path thin-film evaporation for separating the reaction products.

Die bekannten Verfahren sind somit sowohl mit sehr hohem technischen Aufwand verbunden als auch unzureichend für das Altölgemisch, das an den Sammelstellen zur Regenerierung zusammengeführt wird und beliebige Komponenten enthält.The known methods are therefore both very expensive and inadequate for the waste oil mixture, which is brought together at the collection points for regeneration and contains any components.

Der Erfindung liegt die Aufgabe zugrunde, ein universell einsetzbares Verfahren zu entwickeln, das gestattet, Schadstoffe und sonstige unerwünschte Bestandteile aus gebrauchten Schmierölen und sonstigen Altölen mit höheren Produktausbeuten und höherer Produktqualität bei geringerem Verfahrensaufwand und insbes. geringerem Deponieanfall als nach dem Stand der Technik möglich zu entfernen. Das Verfahren soll insbesondere geeignet sein für spezielle Behandlungen, die Hydrierung oder etwa die Behandlung mit Natrium einzubeziehen und verfahrenstechnisch Vereinfachungen und hierdurch bedingte Kostenreduzierungen, etwa durch Vermeidung der Katalysatorvergiftung bei einer eingeschalteten Hydrierstufe, herbeizuführen.The invention has for its object to develop a universally applicable method that allows pollutants and other undesirable components from used lubricating oils and other waste oils with higher product yields and higher product quality with less process effort and in particular less landfill than what is possible according to the prior art remove. The process is said to be particularly suitable for special treatments, the hydrogenation or, for example, the treatment with sodium and to bring about simplifications in terms of process technology and the associated cost reductions, for example by avoiding catalyst poisoning when the hydrogenation stage is switched on.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man Altöle nach einer Grobfiltrierung

  • (1) auf eine Temperatur von 50 bis 100 °C in einem geschlossenen Rührwerk erhitzt und unter intensivem Rühren jeweils bezogen auf das Altöl versetzt mit 0,5 bis 2,5 Gew.% einer wäßrigen Alkaliwasserglaslösung mit einem Wassergehalt von 30 bis 70 Gew.%, bezogen auf die Lösung, und 0,25 bis 2,5 Gew.% einer wäßrigen Lösung eines Polyalkylenglykols der Formel
    Figure imgb0001
     mit R = n-Alkyl mit 8 bis 20 Kohlenstoffatomen, R₁ = Wasserstoff, Alkyl mit 1 bis 3 Kohlenstoffatomen, n = 20 bis 125 und einem durchschnittlichen Molekulargewicht von 1.000 bis 10.000, sowie einem Wassergehalt von 80 bis 97,5 Gew.%, bezogen auf die Lösung,
  • (2) das erhaltene Gemisch in einem Dekanter bei 70 bis 90°C absetzen läßt, das sedimentierte Material abgetrennt und
  • (3) aus der Ölphase bei einer Temperatur von 100 bis 140°C und einem Druck von 2,7 kPa bis 13,3 kPa (20 bis 100) Torr die aus Wasser und Lösungsmittel bestehenden Leichtsieder abtrennt.
This object is achieved in that waste oils after a coarse filtration
  • (1) heated to a temperature of 50 to 100 ° C in a closed agitator and mixed with intensive stirring based on the waste oil with 0.5 to 2.5% by weight of an aqueous alkali water glass solution with a water content of 30 to 70%. %, based on the solution, and 0.25 to 2.5% by weight of one aqueous solution of a polyalkylene glycol of the formula
    Figure imgb0001
     with R = n-alkyl having 8 to 20 carbon atoms, R₁ = hydrogen, alkyl having 1 to 3 carbon atoms, n = 20 to 125 and an average molecular weight of 1,000 to 10,000, and a water content of 80 to 97.5% by weight, based on the solution,
  • (2) the mixture obtained can settle in a decanter at 70 to 90 ° C, the sedimented material separated and
  • (3) from the oil phase at a temperature of 100 to 140 ° C and a pressure of 2.7 kPa to 13.3 kPa (20 to 100) torr separates the low boilers consisting of water and solvent.

In der Verfahrensstufe (2) findet insbesondere eine Entwässerung statt. Die Einsatzstoffe binden das Wasser als Rückstandsschlamm, der dann durch Separation in bekannter Weise abgetrennt wird. 50 bis 80 % des im Altöl vorhandenen freien Wassers werden auf diese Weise abgetrennt. Die Entfernung des Restwassers und der Leichtsieder erfolgt sodann destillativ in der Verfahrensstufe (3). Die Altölbehandlung nach den Verfahrensstufen (1) bis (3) erfolgt in einem Temperaturbereich von 50 bis 140°C, wobei möglichst tiefe Temperaturen dieses Bereichs bevorzugt sind. In der Stufe (3) ist eine PCB-Anreicherung in den Leichtsiedern und Wasser ausgeschlossen, da der Siedepunktsbereich von polychlorierten Bi- und Terphenylen oberhalb der Stripptemperatur liegt. Eine PCB-Abtrennung erfolgt daher in der Verfahrensstufe (3) nicht, womit gewährleistet ist, daß die nach diesem Verfahren erhaltenen Leichtsieder und Wasser nicht mit PCB belastet sind. Dies ist für ein umweltfreundliches Verfahren für Altölaufarbeitung von großer Bedeutung.In process stage (2), dewatering takes place in particular. The feed materials bind the water as residue sludge, which is then separated in a known manner by separation. 50 to 80% of the free water present in the waste oil is separated in this way. The residual water and the low boilers are then removed by distillation in process step (3). The waste oil treatment according to process steps (1) to (3) takes place in a temperature range from 50 to 140 ° C, with temperatures as low as possible being preferred in this range. In stage (3), PCB accumulation in the low boilers and water is excluded, since the boiling point range of polychlorinated bi- and terphenylene is above the stripping temperature. PCB separation therefore does not take place in process stage (3), which ensures that the low boilers and water obtained by this process are not contaminated with PCB. This is of great importance for an environmentally friendly process for waste oil processing.

Verfahrensstufe 3 kann auch vor Verfahrensstufe 2 durchgeführt werden, indem zunächst die Leichtsieder aus dem erhaltenen Gemisch abgetrennt, sodann in einem Dekanter absetzen gelassen und schließlich das sedimentierte Material abgetrennt wird.Process stage 3 can also be carried out before process stage 2 by first separating the low boilers from the mixture obtained, then letting them settle in a decanter and finally separating the sedimented material.

Vorzugsweise werden in Verfahrensstufe (1) die Alkaliwasserglaslösungen und/oder die Polyalkylenglykollösungen vorgewärmt insbesondere auf 30 bis 60°C, bevorzugt auf etwa 50°C.In process stage (1), the alkali water glass solutions and / or the polyalkylene glycol solutions are preferably preheated, in particular to 30 to 60 ° C., preferably to about 50 ° C.

Eine Alternative in der Verfahrensführung besteht darin, man in der Verfahrenstufe (1) auf eine Temperatur von 60 bis 80°C in einem geschlossenen Rührwerk erhitzt und unter intensivem Rühren jeweils bezogen auf das Altöl versetzt mit 0,5 bis 2,5 Gew.% einer wäßrigen Alkaliwasserglaslösung mit einem Wassergehalt von 30 bis 70 Gew.%, bezogen auf die Lösung, und 0,25 bis 2,5 Gew.% einer wäßrigen Lösung eines Polyalkylenglykols der Formel

Figure imgb0002

mit R₂ = n-Alkyl mit 10 bis 14-Kohlenstoffatomen, n= 21 bis 30 und einem durchschnittlichen Molekulargewicht von 2.000 bis 5.000 mit einem Wassergehalt von 80 bis 97,5 Gew.%, bezogen auf die Lösung.An alternative method of operation is to heat in process stage (1) to a temperature of 60 to 80 ° C. in a closed agitator and, with intensive stirring, to add 0.5 to 2.5% by weight, based on the waste oil. an aqueous alkali water glass solution with a water content of 30 to 70% by weight, based on the solution, and 0.25 to 2.5% by weight of an aqueous solution of a polyalkylene glycol of the formula
Figure imgb0002
with R₂ = n-alkyl having 10 to 14 carbon atoms, n = 21 to 30 and an average molecular weight of 2,000 to 5,000 with a water content of 80 to 97.5% by weight, based on the solution.

Nach einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens behandelt man die nach den Verfahrensschritten (1) bis (3) vorbehandelte Ölphase weiter, indem man

  • (4) die Ölphase bei einer Temperatur von 30 bis 120 °C mit 3 bis 8 Gewichtsteilen n-Alkanen mit 6 bis 10 Kohlenstoffatomen auf 1 Gewichtsteil der vorbehandelten Ölphase versetzt, unter Beibehaltung der Temperatur für eine Weile intensiv rührt, das erhaltene Gemisch in einem Dekanter bei Raumtemperatur absetzen läßt, das sedimentierte Material abtrennt, die Ölphase in einem Adsorber mit Filtereinsatz behandelt, wobei der Filtereinsatz Bleicherden oder kompaktiertes Aluminiumoxid enthält, und
  • (5) aus dem erhaltenen Ölfiltrat bei einer Temperatur von 50 bis 80 °C und einem Druck von 2,7 kPa bis 13,3 kPa (20 bis 100 Torr) die Leichtsieder (n-Alkane) abtrennt.
    Eine weitere Ausgestaltung des erfindungsgemäßen Verfahrens insbesondere zur Behandlung von polychlorierte Bi- und Terphenyle enthaltenden Altölen besteht darin, daß man die durch die Verfahrensschritte (1) bis (3) vorbehandelte Ölphase weiterbehandelt, indem man
  • (6) die vorbehandelte Altölphase auf eine Temperatur von 70 bis 120 °C in einem geschlossenen Rührwerk erhitzt und mit 3 bis 8 Gewichtsteilen n-Alkanen mit 6 bis 10 Kohlenstoffatomen auf 1 Gewichtsteil der vorbehandelten Altölphase versetzt, unter intensivem Rühren jeweils bezogen auf die vorbehandelte Altölphase versetzt mit 0,1 bis 0,5 Gew.% einer wäßrigen Alkaliwasserglaslösung mit einer pH-Wert ≧ 9 und 0,1 bis 0,5 Gew.% Polyalkylenglykol der allgemeinen Formel
    Figure imgb0003
     mit R₃ = Wasserstoff oder Methyl, n = 9 bis 22, einer Hydroxylzahl von 100 bis 300 mg K0H/g nach DIN 53240 und einem durchschnittlichen Molekulargewicht von 380 bis 1.050, unter Beibehaltung der Temperatur eine Weile,15 bis 120 Minuten, insbesondere 30 bis 100 Minuten und bevorzugt etwa 50 bis 60 Minuten, intensiv rührt, 0,1 bis 0,25 Gew.% wasserfreiem Alkali-metasilikat, bezogen auf die Altölphase, zugibt, nochmals 5 bis 15 Minuten rührt,
  • (7) das erhaltene Gemisch in einem Dekanter bei Raumtemperatur absetzen läßt, das sedimentierte Material abtrennt,
  • (8) die Ölphase bei einer Temperatur von 30-60°C in einem Adsorber, vorzugsweise einem Perkolationsadsorber, mit Filtereinsatz behandelt, wobei der Filtereinsatz Bleicherden oder kompaktiertes Aluminiumoxid enthält, und
  • (9) aus dem Ölfiltrat bei einer Temperatur von 50 bis 80°C und einem Druck von 2,7 kPa bis 13,3 kPa (20 bis 100 Torr) die Leichsieder (n-Alkane) abtrennt.
According to a further embodiment of the process according to the invention, the oil phase pretreated according to process steps (1) to (3) is further treated by:
  • (4) the oil phase at a temperature of 30 to 120 ° C with 3 to 8 parts by weight of n-alkanes with 6 to 10 carbon atoms to 1 part by weight of the pretreated oil phase, while maintaining the temperature for a while stirring vigorously, the mixture obtained in one Let the decanter settle at room temperature, the sedimented material is separated off, the oil phase is treated in an adsorber with a filter insert, the filter insert containing bleaching earth or compacted aluminum oxide, and
  • (5) the low boilers (n-alkanes) are separated off from the oil filtrate obtained at a temperature of 50 to 80 ° C. and a pressure of 2.7 kPa to 13.3 kPa (20 to 100 torr).
    A further embodiment of the process according to the invention, in particular for the treatment of waste oils containing polychlorinated bi- and terphenyls, consists in further treating the oil phase pretreated by process steps (1) to (3) by
  • (6) the pretreated waste oil phase is heated to a temperature of 70 to 120 ° C in a closed agitator and mixed with 3 to 8 parts by weight of n-alkanes with 6 to 10 carbon atoms to 1 part by weight of the pretreated waste oil phase, with intensive stirring in each case based on the pretreated The waste oil phase is mixed with 0.1 to 0.5% by weight of an aqueous alkali water glass solution with a pH ≧ 9 and 0.1 to 0.5% by weight of polyalkylene glycol of the general formula
    Figure imgb0003
     with R₃ = hydrogen or methyl, n = 9 to 22, a hydroxyl number of 100 to 300 mg K0H / g according to DIN 53240 and an average molecular weight of 380 to 1,050, while maintaining the temperature for a while, 15 to 120 minutes, especially 30 to 100 minutes and preferably about 50 to 60 minutes, stirred vigorously, 0.1 to 0.25% by weight of anhydrous alkali metasilicate, based on the waste oil phase, is added, stirring is continued for 5 to 15 minutes,
  • (7) the mixture obtained is allowed to settle in a decanter at room temperature and the sedimented material is separated off,
  • (8) treating the oil phase with a filter insert at a temperature of 30-60 ° C. in an adsorber, preferably a percolation adsorber, the filter insert containing bleaching earth or compacted aluminum oxide, and
  • (9) the low boilers (n-alkanes) are separated from the oil filtrate at a temperature of 50 to 80 ° C. and a pressure of 2.7 kPa to 13.3 kPa (20 to 100 torr).

Bevorzugt setzt man in Verfahrensstufe (6) 0,1 bis 0,5 Gew.%, bezogen auf die Altölphase Polyäthylenglykol der allgemeinen Formel

Figure imgb0004

ein, mit n = 9 bis 22, einer Hydroxylzahl von mg KOH/g 100 bis 300 und insbesondere 170 bis 210 nach DIN 53240 und einem durchschnittlichen Molekulargewicht von 380 bis 1050, und insbesondere 480 bis 650 ein.Process stage (6) preferably uses 0.1 to 0.5% by weight, based on the waste oil phase, of polyethylene glycol of the general formula
Figure imgb0004
a, with n = 9 to 22, a hydroxyl number of mg KOH / g 100 to 300 and in particular 170 to 210 according to DIN 53240 and an average molecular weight of 380 to 1050, and in particular 480 to 650.

Zwischen Verfahrensstufe (3) und Verfahrensstufe (4) kann in einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens eine an sich bekannte Hydrierbehandlungsstufe eingeschaltet werden, worin in Gegenwart eines hydrieraktiven Katalysators insbesondere bei 200 bis 400 °C und 10 bis 200 10⁵ Pa (10 bis 200 bar) und vorzugsweise bei 300 bis 380 °C und 40 bis 60 10⁵ Pa (40 bis 60 bar) die vorbehandelte Ölphase hydriert wird. Diese Einbeziehung bekannter Hydrierverfahren wird in der Regel jedoch nur dann wirtschaftlich sinnvoll sein, wenn das erfindungsgemäße Verfahren in einer bereits bestehenden Hydrieranlage zur Anwendung kommen soll.In a further embodiment of the process according to the invention, a hydrogenation treatment step known per se can be switched between process step (3) and process step (4), in which, in the presence of a hydrogenation-active catalyst, in particular at 200 to 400 ° C. and 10 to 200 10⁵ Pa (10 to 200 bar ) and preferably at 300 to 380 ° C and 40 to 60 10⁵ Pa (40 to 60 bar) the pretreated oil phase is hydrogenated. However, this inclusion of known hydrogenation processes will generally only make economic sense if the process according to the invention is to be used in an already existing hydrogenation plant.

Der Filtereinsatz der Verfahrensstufe (4) bzw. (8) wird bedarfsweise regeneriert, indem man ihn mit einem Lösungsmittel vom adsorbierten Material freiwäscht. Vorzugsweise wird hierfür ein Keton-Lösungsmittel eingesetzt, das insbesondere aus einem oder mehreren Lösungsmitteln mit jeweils einem Siedepunkt von 50 bis zu 80°C besteht und insbesondere Azeton oder Methylethylketon ist.The filter insert of process stage (4) or (8) is regenerated if necessary by washing it free of the adsorbed material with a solvent. A ketone solvent is preferably used for this purpose, which in particular consists of one or more solvents each having a boiling point of 50 to 80 ° C. and is in particular acetone or methyl ethyl ketone.

Nach einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens wird die behandelte Ölphase abschließend einer Vakuumdestillation bei einer Temperatur von 200 bis 300 °C und einem Druck von 0,13 kPa bis 6,67 kPa (1 bis 50 Torr) unterworfen.According to a further embodiment of the process according to the invention, the treated oil phase is finally subjected to vacuum distillation at a temperature of 200 to 300 ° C. and a pressure of 0.13 kPa to 6.67 kPa (1 to 50 torr).

Zur Behandlung von Altölen, die polychlorierte Bi- und Terphenyle enthalten, ist nach einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens vorgesehen, nach der Verfahrensstufe (3) in an sich bekannter Weise eine Behandlung der trockenen Ölphase (mit Wassergehalten < 0,1 Gew.%) mit feindispergiertem Natrium einzuschalten. Die Verfahrensstufen (1) bis (3) sind in der Lage, einen konstanten wasserfreien Ölstrom zu liefern, der die wichtigste Voraussetzung für den Natriumeinsatz ist. Da bei diesem wasserfreien Ölstrom die Oxidationprodukte und die Nicht-PCB-Chlorverbindungen zum großen Teil durch die Vorbehandlung entfernt sind, ergibt sich eine gute Wirtschaftlichkeit für das Natriumverfahren.For the treatment of waste oils containing polychlorinated bi- and terphenyls, a further embodiment of the process according to the invention provides for treatment of the dry oil phase (with water contents <0.1% by weight) in a manner known per se after process step (3). with finely dispersed sodium. Process steps (1) to (3) are able to deliver a constant water-free oil flow, which is the most important requirement for the use of sodium. Since the oxidation products and the non-PCB chlorine compounds are largely removed by the pretreatment in this water-free oil stream, the sodium process is economically viable.

Das für die Altölbehandlung notwendige Natrium wird in der Form einer Dispersion, insbesondere bestehend aus Natriumteilchen von 5 bis 10 µm, in einem Basisöl von ähnlicher Zusammensetzung wie Motorenöle dem vorbehandelten Altöl zugesetzt. Zu diesem Zweck wird in einem Disper- gator Natrium in einem Öl, vorzugsweise Reraffinat, aufgeschmolzen und fein zerteilt, so daß Teilchengrößen von < 20 µm erreicht werden. Eine Dispersion von 33 Gew.% Natrium ist für die Behandlung des vorbehandelten trockenen Ölstromes besonders geeignet. Die Zugabemenge der Dispersion wird auf den Gehalt anorganisch gebundenem Chlor abgestimmt. Die Behandlungstemperatur und -zeit richten sich nach der Qualität des Trockenöles. Normalerweise kann in einem Temperaturbereich von 20°C bis 250°C und insbesondere in einem Temperaturbereich von 100 bis 200°C und in einem Zeitraum von 1 bis 30 Minuten eine zuverlässige PCB-Abtrennung erzielt werden.The sodium required for the waste oil treatment is added to the pretreated waste oil in the form of a dispersion, in particular consisting of sodium particles of 5 to 10 μm, in a base oil of a similar composition to motor oils. For this purpose, sodium in an oil, preferably reraffinate, is melted and finely divided in a disperser, so that particle sizes of <20 μm are achieved. A dispersion of 33% by weight sodium is particularly suitable for the treatment of the pretreated dry oil stream. The amount of dispersion added is matched to the content of inorganic chlorine. The treatment temperature and time depend on the quality of the drying oil. Normally, a temperature range from 20 ° C to 250 ° C and especially in a temperature range from 100 to 200 ° C and in a period of 1 to 30 minutes reliable PCB separation can be achieved.

Bei der Behandlung des Altöles mit Natrium entsteht Natriumchlorid, verunreinigt mit Metalloxiden, Metallcarbonaten und Metallsulfaten. Diese ölhaltigen Feststoffe werden abgetrennt, etwa durch Sedimentation in einem Separator oder Dekanter. Die Ölphase, die nunmehr frei von PCB's und Chlor ist, wird der Behandlung gemäß Verfahrensstufe (4) unterworfen und anschließend destilliert.Treatment of the waste oil with sodium produces sodium chloride, contaminated with metal oxides, metal carbonates and metal sulfates. These oily solids are separated, for example by sedimentation in a separator or decanter. The oil phase, which is now free of PCB's and chlorine, is subjected to the treatment according to process step (4) and then distilled.

Bei dem erfindungsgemäßen Verfahren handelt es sich um ein mildes und umweltfreundliches Verfahren. Gleichzeitig wird eine kostengünstige und einfache Prozeß- und Apparatetechnik gewährleistet. In den einzelnen Verfahrensschritten der Vorbehandlung verlaufen parallel mehrere physikalische und chemische Vorgänge. Sowohl die Entfernung von allen Schadstoffen als auch die Aufbereitung laufen unter milden Prozeßbedingungen. Hierbei ist die "filtrierende Adsorption" von besonderer Bedeutung für die Reinigung des zu regenerierenden Materials. Die Verfahrensschritte des erfindungsgemäßen Verfahrens sind:

  • Ausflockung und Umwandlung von dispersen Verunreinigungen
  • Adsorption und sedimentation der ausgeflockten und umgewandelten Verunreinigungen
  • filtrierende Adsorption zur selektiven Trennung von gelösten und ungelösten feindispersen Verunreinigungen wie z.B. Abbauprodukte, Oxidationsprodukte, Additiven
  • Destillation bzw. Abstreifen der Stoffe außerhalb des Siedebereichs der Schmieröle
The method according to the invention is a mild and environmentally friendly method. At the same time, an inexpensive and simple process and apparatus technology is guaranteed. In the individual process steps of the pretreatment, several physical and chemical processes run in parallel. Both the removal of all pollutants and the preparation run under mild process conditions. Here, the "filtering adsorption" is of particular importance for the cleaning of the material to be regenerated. The process steps of the process according to the invention are:
  • Flocculation and conversion of dispersed contaminants
  • Adsorption and sedimentation of the flocculated and converted impurities
  • Filtering adsorption for the selective separation of dissolved and undissolved, finely dispersed impurities such as degradation products, oxidation products, additives
  • Distillation or stripping of the substances outside the boiling range of the lubricating oils

Das gewonnene Grundöl zeichnet sich durch einen günstigeren und höheren Viskositätsindex als Frischöl aus. Alle aschebildenden Additive - sonst Verursacher von Schlammbildungwerden entfernt, d. h. der Aschegehalt ist praktisch 0 Gew.%. Die Viskositätsverbesserungs-Additive bleiben weitgehend erhalten, und zwar etwa zumindest 1/3 der entsprechenden Additive des Frischadditiv-Packages.The base oil obtained is characterized by a cheaper and higher viscosity index than fresh oil. All ash-forming additives - otherwise the cause of sludge formation are removed, i.e. H. the ash content is practically 0% by weight. The viscosity improvement additives are largely retained, namely at least 1/3 of the corresponding additives in the fresh additive package.

Verunreinigungen in Altöl bilden durch anwesende Detergentien stabile Dispersionen. Additive verhindern die physikalische Abtrennung der Verunreinigungen durch Schwer- und/oder Zentrifugalkraft. Erfindungsgemäß destabilisieren in Verfahrensstufe (1) die Flockungs- und Adsorptionsmittel, nämlich Alkaliwasserglas und Polyalkylenglykol der angegebenen Formel, die Dispersion. Damit werden die Dichteunterschiede zwischen Öl- und Fremdstoffphase wirksam. Parallel hierzu erfolgt eine chemische Umwandlung der Chlorverbindungen und die Bildung von NaCl sowie nicht-chlorierter Verbindungen. Die Oxydationsprodukte werden neutralisiert und die umgewandelten sowie neutralisierten Produkte werden adsorbiert.Contaminants in waste oil form stable dispersions due to the presence of detergents. Additives prevent the physical separation of the contaminants by gravity and / or centrifugal force. According to the invention, the flocculation and adsorbents, namely alkali water glass and polyalkylene glycol of the formula given, destabilize the dispersion in process step (1). The differences in density between the oil and foreign matter phases are effective. At the same time, the chlorine compounds are chemically converted and NaCl and non-chlorinated compounds are formed. The oxidation products are neutralized and the converted and neutralized products are adsorbed.

In Verfahrensstufe (2) werden Verunreinigungen und die Flockungs- und Adsorptionsmittel abgetrennt. Die ausgeflockten, dispergierten Verunreinigungen werden infolge der in Stufe (1) erfolgten Destabilisierung und des in der Stufe (1) wirksam gewordenen Dichteunterschiede durch die Wirkung der Schwerkraft oder von minimalen Zentrifugalkräften mittels Dekantern oder Separatoren ausgeschieden.In process stage (2), impurities and the flocculants and adsorbents are separated off. The flocculated, dispersed impurities are eliminated by decanters or separators as a result of the destabilization which took place in stage (1) and the density differences which became effective in stage (1) by the action of gravity or minimal centrifugal forces.

In Verfahrensstufe (3) werden die Leichtsieder, nämlich polare und unpolare Lösungsmittel, sowie Wasser entfernt.In process stage (3), the low boilers, namely polar and non-polar solvents, and water are removed.

Der Lösungsmittel- und Adsorptionsmittelzusatz in Verfahrensstufe (6) dient zur weiteren Ausfällung von fein dispergierten Verunreinigungen, wobei hier diese Zusätze die Entfernung von polychlorierten Bi- und Terphenylen herbeiführen und der Lösungsmittelzusatz die später folgende Stufe der filtrierenden Adsorption unterstützt. Sind keine polychlorierten Bi- und Terphenyle vorhanden, so kann unter Zusatz der n-Alkane ohne die weitere Zugabe von Adsorptionsmitteln direkt in die Stufe der filtrierenden Adsorption gegangen werden - siehe Verfahrensstufe (4).The solvent and adsorbent additive in process step (6) is used for the further precipitation of finely dispersed impurities, here these additives bring about the removal of polychlorinated bi- and terphenylene and the solvent additive supports the subsequent filtering adsorption step. If there are no polychlorinated bi- and terphenyls, the addition of the n-alkanes can be used to go directly to the filtering adsorption stage without the further addition of adsorbents - see process stage (4).

Der Verfahrensstufe (6) mit Lösungsmittel- und Adsorptionsmittelzusatz folgt die Verfahrensstufe (7), die weitgehend der Verfahrensstufe (2) entspricht.Process stage (6) with the addition of solvent and adsorbent is followed by process stage (7), which largely corresponds to process stage (2).

In der Verfahrensstufe (8) bzw. (4) erfolgt die filtrierende Adsorption. In dieser Stufe werden gezielt die restlichen gelösten und ungelösten Verunreinigungen sowie unerwünschten Restadditive an die Adsorbentien gebunden. Die Schmierölkomponenten (Kohlenwasserstoffe) passieren die Adsorbentien. Bei dieser filtrierenden Adsorption handelt es sich um eine Vielparameter-Trennmethode, die dadurch gekennzeichnet ist, daß zwei chemisch verschiedene Stoffe oder zwei chemisch verschiedene Stoffgruppen aufgrund ihres unterschiedlichen Adsorptionsvermögens voneinander getrennt werden, indem man ein bestimmtes Lösungsmittel und ein Adsorbens auf das Gemisch einwirken läßt. Gegenüber der üblichen Filtration unterscheidet sich die filtrierende Adsorption dadurch, daß bei der Trennung nur eine einzige Phase vorliegt, während die Filtration zwei Phasen, in der Regel fest/flüssig, voraussetzt. Gegenüber der normalen Adsorption ist die filtrierende Adsorption durch ihre Selektivität, die durch das selektive Lösungsmittel und ein ausgesuchtes Adsorbens, hier Bleicherden oder kompaktiertes Aluminiumoxid, erreicht wird, unterschieden, siehe "Filtrierende Adsorption", W. Fuchs, F. Glaser und E. Bendel, Chemie-Ingenieurtechnik 1959, Seiten 677 679.The filtering adsorption takes place in process stage (8) or (4). In this stage, the remaining dissolved and undissolved impurities and unwanted residual additives are specifically bound to the adsorbents. The lubricating oil components (hydrocarbons) pass through the adsorbents. This filtering adsorption is a multi-parameter separation method, which is characterized in that two chemically different substances or two chemically different groups of substances are separated from one another due to their different adsorption capacity, by allowing a specific solvent and an adsorbent to act on the mixture. Compared to conventional filtration, the filtering adsorption differs in that there is only a single phase during the separation, while the filtration requires two phases, generally solid / liquid. Compared to the normal Adsorption is the filtering adsorption distinguished by its selectivity, which is achieved by the selective solvent and a selected adsorbent, here bleaching earth or compacted aluminum oxide, see "Filtering adsorption", W. Fuchs, F. Glaser and E. Bendel, chemistry Engineering technology 1959, pages 677 679.

Adsorbiertes Material, nämlich 5 bis 10 Gew.% fein dispergierte, gelöste Oxydationsprodukte und Restadditive werden mit geeigneten Lösungsmitteln, Lösungsmittel mit einem Siedepunkt von bis zu 80°C, insbesondere Aceton oder Methylethylketon, desorbiert. Das Adsorbens wird bei etwa 60 bis etwa 120°C, vorzugsweise etwa 100°C, unter Schutzgas, vorzugsweise Stickstoff, getrocknet und dannach auf die erforderliche Temperatur für die Verfahrensstufe (8) gebracht. Damit ist das Adsorbens wieder einsatzbereit, und kann auf diese Werte ständig benutzt werden.
Die Schmierölbestandteile (etwa 1,5 Gew.%), die im Adsorbens enthalten sind, werden vor der Adsorbensregenerierung (mit Aceton oder Methylethylketon) durch Lösungsmittelspülung, insbesondere mit n-Heptan, herausgelöst und der Verfahrensstufe (6) oder (9) zugeführt. Dieser Schritt-dient zur Erhöhung der Ausbeute des Regenerats.
Die nach dem Abdampfen des Lösungsmittels anfallenden Restadditive und Oxydationsprodukte finden als Zusatzstoffe z.B. für die Asphalt-Verarbeitung Verwendung. PCB's, chlorierte Dioxine, Furane und Aliphate mit Chlorgehalten > 5 % können auf diese Weise bis unter die Nachweisgrenze abgebaut werden. Das rückgewonnene Lösungsmittel wird wieder zur Lösungsmittelspülung eingesetzt.Adsorbed material, namely 5 to 10% by weight of finely dispersed, dissolved oxidation products and residual additives, are desorbed with suitable solvents, solvents with a boiling point of up to 80 ° C., in particular acetone or methyl ethyl ketone. The adsorbent is dried at about 60 to about 120 ° C., preferably about 100 ° C., under a protective gas, preferably nitrogen, and then brought to the temperature required for process step (8). The adsorbent is now ready for use again and can be used continuously at these values.
The lubricating oil constituents (about 1.5% by weight) which are contained in the adsorbent are dissolved out before the adsorbent regeneration (with acetone or methyl ethyl ketone) by solvent rinsing, in particular with n-heptane, and fed to process stage (6) or (9). This step serves to increase the yield of the regrind.
The residual additives and oxidation products obtained after evaporation of the solvent are used as additives, for example for asphalt processing. PCBs, chlorinated dioxins, furans and aliphates with chlorine contents> 5% can be broken down below the detection limit in this way. The recovered solvent is used again for solvent rinsing.

In der Verfahrensstufe (5) bzw. (9) wird das Lösungsmittel vom Regenerat getrennt und in Stufe (4) bzw. (6) zurückgeführt.In process step (5) or (9), the solvent is separated from the regenerate and returned in step (4) or (6).

Handelt es sich bei der abschließend erhaltenen Ölphase um ein Gemisch von Schmierölfraktionen mit unterschiedlichen Flammpunkten und Viskositäten, so müssen die Fraktionen unter Vakuum und Temperaturen über 200°C getrennt werden. Der Sumpf ist Grundöl.If the final oil phase is a mixture of lubricating oil fractions with different flash points and viscosities, the fractions must be separated under vacuum and temperatures above 200 ° C. The swamp is base oil.

Das die Verfahrensschritte (1) bis (3) umfassende Verfahren kann insofern für eine dezentrale Altölaufbereitung genutzt werden, als die gesammelten Altöle in Gebietssammelstellen zusammengeführt und in dezentralen Kleinanlagen nach dem die Verfahrensschritte (1) bis (3) umfassenden Verfahren als Teilverfahren behandelt werden. Das auf diese Weise behandelte Altöl kann dann in einer zentralen Großanlage den Verfahren nach einem oder mehreren der Unteransprüche insbesondere zur Entfernung von Chlorverbindungen und perchlorierten Bi- und Terphenylen unterworfen werden.The process comprising process steps (1) to (3) can be used for decentralized waste oil processing, in that the collected waste oils are brought together in area collection points and treated in decentralized small plants according to the process comprising process steps (1) to (3) as a partial process. The waste oil treated in this way can then be subjected to the process according to one or more of the subclaims, in particular for the removal of chlorine compounds and perchlorinated bi- and terphenylene, in a central large-scale plant.

Die folgenden Einsatzstoffe finden bevorzugt Anwendung:

  • 1. als Alkaliwasserglas
       Natriumwasserglas 50/51 in Verfahrensstufe (1) und Verfahrensstufe (6), alkalisch, filtriert Analysenwerte
    H₂O
    54,4 - 55,4 %
    SiO₂
    30 - 30,5 %
    Na₂0
    14,6 - 15,1 %
    η mPas/20 °C
    400 - 600
    ρ kg/m³, 20 °C
    1530.
    Natriumwasserglas 58/60 in Verfahrensstufe (1), filtriert
    H₂0
    45,5 %
    Si0₂
    36,5 %
    Na₂0
    18,0 %
    η mPas/20 °C
    über 10.000
    ρ kg/m³, 20 °C
    1710
  • 2. als Alkali-metasilikat in Verfahrensstufe (6), wasserfrei
       Analysenwerte
    Si0₂
    48± 1,0 %
    Na₂0
    51± 1,0 %
  • 3. als Polyalkylenglykol (nicht ionogen) in Verfahrensstufe (1)
    Polypropylenglykol mit C₁₂H₂₅-Endgruppen, durchschnittliches Molekulargewicht 2.000 bis 10.000
    Lösungen wirksam im Konzentrationsbereich 2,5 bis 20 Gew.%.
  • 4. als Polyalkylenglykol in Verfahrensstufe (6)
    Polyäthylenglykol (PEG)
    Hydroxylzahl 100 bis 300 mg K0H/g nach DIN 53240 mit mittlerem Molekulargewicht 380 bis 1050.
  • 5. als Lösungsmittel in Verfahrensstufen (4) und (6) n-Alkane, C₆ - C₁₀, insbesondere n-Heptan, technisches Produkt.
  • 6. als Adsorbentien in Verfahrensstufen (4) und (8)
    TONSIL CCG 30/60 mesh und TONSIL LFF 80
    Korngrößenverteilung: breit < 0,25 mm bis > 0,55 mm chemische Zusammensetzung:
       SiO₂, Al₂0₃, Fe₂0₃, Mg0, Ca0, Na₂0 und K₂0.
    COMPALOX, kompaktiertes Aluminiumoxid
    Korngröße 1,5 bis 5 mm
    spezifische Oberfläche 180 bis 200 m²/g
    chemische Zusammensetzung:
       Al₂0₃(92 %), Si0₂(0,01 - 0,02 %), Fe₂0₃(0,01 - 0,03 %, Na₂0(0,4 - 0,6 %)
The following feedstocks are preferred:
  • 1. as an alkali water glass
    Sodium water glass 50/51 in process stage (1) and process stage (6), alkaline, filters analytical values
    H₂O
    54.4 - 55.4%
    SiO₂
    30 - 30.5%
    Na₂0
    14.6 - 15.1%
    η mPas / 20 ° C
    400-600
    ρ kg / m³, 20 ° C
    1530.
    Sodium water glass 58/60 in process step (1), filtered
    H₂0
    45.5%
    Si0₂
    36.5%
    Na₂0
    18.0%
    η mPas / 20 ° C
    over 10,000
    ρ kg / m³, 20 ° C
    1710
  • 2. as alkali metasilicate in process step (6), anhydrous
    Analytical values
    Si0₂
    48 ± 1.0%
    Na₂0
    51 ± 1.0%
  • 3. as polyalkylene glycol (non-ionic) in process step (1)
    Polypropylene glycol with C₁₂H₂₅ end groups, average Molecular weight 2,000 to 10,000
    Solutions effective in the concentration range 2.5 to 20% by weight.
  • 4. as polyalkylene glycol in process step (6)
    Polyethylene glycol (PEG)
    Hydroxyl number 100 to 300 mg K0H / g according to DIN 53240 with average molecular weight 380 to 1050.
  • 5. as a solvent in process stages (4) and (6) n-alkanes, C₆ - C₁₀, especially n-heptane, technical product.
  • 6. as adsorbents in process stages (4) and (8)
    TONSIL CCG 30/60 mesh and TONSIL LFF 80
    Grain size distribution: wide <0.25 mm to> 0.55 mm chemical composition:
    SiO₂, Al₂0₃, Fe₂0₃, Mg0, Ca0, Na₂0 and K₂0.
    COMPALOX, compacted aluminum oxide
    Grain size 1.5 to 5 mm
    specific surface area 180 to 200 m² / g
    chemical composition:
    Al₂0₃ (92%), Si0₂ (0.01 - 0.02%), Fe₂0₃ (0.01 - 0.03%, Na₂0 (0.4 - 0.6%)

Adsorbensregenerierung mit Aceton, Methylethylketon (technisch).Adsorbent regeneration with acetone, methyl ethyl ketone (technical).

Eingesetzte Filter: Edelstahl, Siebgewebe 20 µm bis 200 µm; Glasfaserfilter und Faservliesfilter.Filters used: stainless steel, sieve mesh 20 µm to 200 µm; Glass fiber filter and non-woven filter.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.

Beispiel 1example 1

95 Teile Altöl eines Gemischs von Sammelstellen wurde nach einer Grobfiltrierung auf eine Temperatur von 70 °C in einem geschlossenen Rührwerk erhitzt und unter intensivem Rühren jeweils bezogen auf das Altöl mit 2,5 Gew.% einer auf 50°C vorgewärmten wäßrigen Alkaliwasserglaslösung 58/60 mit einem Wassergehalt von 54 Gew.%, bezogen auf die Lösung, und Gew.% einer auf 50°C vorgewärmte wäßrigen 20 Gew.%igen Polypropylenglykollösung (mittleres Molekulargzewicht 3.000) mit einem Wassergehalt von 80 Gew.%, bezogen auf die Lösung, versetzt. Das Gemisch wurde nach der Zugabe der Einsatzstoffe 30 Minuten bei 80 °C intensiv weitergerührt. Das danach erhaltene Gemisch wurde in einem Dekanter bei 70 °C mit einer Durchsatzleistung von 3.000 ml/h sedimentiert und die Ölphase abgetrennt. Aus der Ölphase wurden die Leichtsieder und das Restwasser bei einer Temperatur von 130 °C und einem Druck von 6,67 kPa (50 Torr) abgetrennt.After coarse filtration, 95 parts of waste oil from a mixture of collection points were heated to a temperature of 70 ° C. in a closed agitator and, with intensive stirring, based on the waste oil in each case with 2.5% by weight of an aqueous alkali water glass solution 58/60 preheated to 50 ° C. with a water content of 54% by weight, based on the solution, and% by weight of an aqueous 20% by weight polypropylene glycol solution (average molecular weight 3,000) preheated to 50 ° C. and a water content of 80% by weight, based on the solution, transferred. After the addition of the starting materials, the mixture was stirred vigorously at 80 ° C. for 30 minutes. The mixture obtained was sedimented in a decanter at 70 ° C with a throughput of 3,000 ml / h and the oil phase separated. The low boilers and the residual water were separated from the oil phase at a temperature of 130 ° C. and a pressure of 6.67 kPa (50 torr).

Beispiel 2Example 2

Nicht-PCB-haltiges Altöl wurde als nach Beispiel 1 vorbehandelte, trockene Ölphase in einem geschlossenen Rührwerk mit n-Heptan im Verhältnis Ölphase zu n-Heptan von 1 : 4 Gewichtsteilen versetzt, bei 40 °C 30 Minuten intensiv gerührt. Die Öllösung wurde sodann in einem Dekanter bei 10 bis 20 °C mit einer Durchsatzleistung von 12.000 ml/h sedimentiert, und dann die Öllösung vom Fällungsrückstand abgetrennt.Waste oil not containing PCBs was treated with n-heptane in the ratio of oil phase to n-heptane of 1: 4 parts by weight as a dry oil phase pretreated according to Example 1 in a closed agitator, and stirred intensively at 40 ° C. for 30 minutes. The oil solution was then sedimented in a decanter at 10 to 20 ° C. with a throughput of 12,000 ml / h, and then the oil solution was separated from the precipitation residue.

Beispiel 3Example 3

PCB-haltiges Altöl wurde in einem geschlossenen Rührwerk nach Zumischung von n-Heptan im Verhältnis Ölphase zu n-Heptan von 1 : 4 Gewichtsteilen zur nach Beispiel 1 vorbehandelten Ölphase unter intensivem Rühren bei 80°C mit einer auf 50 °C vorgewärmten Mischung von 0,25 Gew.% Natronwasserglas 50/51 (alkalisch) und 0,1 Gew.% Polyäthylenglykol (mittleres Molekulargewicht 600, OH-Zahl 170 mgKOH/g) jeweils bezogen auf die trockene Ölphase versetzt. Das Gemisch wurde bei 70 °C etwa 110 Minuten intensiv weitergerührt. Danach wurden 0,1 Gew.% wasserfreies Natriummetasilikat zugegeben und weitere 10 Minuten gerührt. Die Öllösung wurde in einem Dekanter bei 10 bis 20 °C mit einer Durchsatzleistung von 12.000 ml/h sedimentiert und die Öllösung vom Rückstand abgetrennt.PCB-containing waste oil was mixed in a closed agitator after the addition of n-heptane in the ratio oil phase to n-heptane of 1: 4 parts by weight to the oil phase pretreated according to Example 1 with intensive stirring at 80 ° C with a mixture of 0 preheated to 50 ° C , 25% by weight soda water glass 50/51 (alkaline) and 0.1% by weight of polyethylene glycol (average molecular weight 600, OH number 170 mgKOH / g), each based on the dry oil phase. The mixture was stirred vigorously at 70 ° C. for about 110 minutes. Then 0.1% by weight of anhydrous sodium metasilicate was added and the mixture was stirred for a further 10 minutes. The oil solution was sedimented in a decanter at 10 to 20 ° C with a throughput of 12,000 ml / h and the oil solution was separated from the residue.

Beispiel 4Example 4

Die Öllösung aus den Beispielen 2 und 3 wurde einer "Filtrierende Adsorption" unterworfen. Der Adsorber bestand aus einem Edelstahlsiebgewebe (20 - 40 µm) und einer Adsorbenspackung mit Bleicherde, Tonsil CCG 30/60. Die Adsorption von unerwünschten Ölbestandteilen erfolgte bei 40 °C. Es wurde mit n-Heptan regeneriert. Der Durchsatz von Regeneratlösung betrug 3.000 ml/h. Aus der Regeneratlösung wurde das Lösungsmittel n-Heptan destillativ bei 70 °C und einem Druck von 6.67 kPa (50 Torr) zurückgewonnen.The oil solution from Examples 2 and 3 was subjected to a "filtering adsorption". The adsorber consisted of a stainless steel screen mesh (20 - 40 µm) and an adsorbent pack with bleaching earth, Tonsil CCG 30/60. The undesired oil components were adsorbed at 40 ° C. It was regenerated with n-heptane. The throughput of regenerated solution was 3,000 ml / h. The solvent n-heptane was recovered from the regenerated solution by distillation at 70 ° C. and a pressure of 6.67 kPa (50 torr).

Bei dem erhaltenen Regenerat handelte es sich um ein Gemisch von Schmierölfraktionen mit unterschiedlichen Flammpunkten und Viskositäten. Die Fraktionen wurden unter Vakuum bei 250 - 300 °C und einem Druck von vor 0,13 kPa bis 1,3 kPa (1 bis 10 Torr) getrennt. Als Sumpf wurde das Grundöl erhalten.The regenerate obtained was a mixture of lubricating oil fractions with different flash points and viscosities. The fractions were separated under vacuum at 250-300 ° C and a pressure of before 0.13 kPa to 1.3 kPa (1 to 10 Torr). The base oil was obtained as the sump.

Zwischenzeitlich wurde der Adsorber regeneriert, indem die adsorbierten Verunreinigungen (Oxidationsprodukte, unerwünschte Restadditive, Abbauprodukte u.s.w.) bei 50 °C mit Aceton (Siedepunkt 56 °C) desorbiert. Der Adsorber wurde unter Stickstoffstrom bei 60 °C getrocknet und wieder verwendbar gemacht.In the meantime, the adsorber has been regenerated by desorbing the adsorbed impurities (oxidation products, unwanted residual additives, degradation products, etc.) at 50 ° C with acetone (boiling point 56 ° C). The adsorber was dried under a stream of nitrogen at 60 ° C. and made reusable.

Die anfallende Acetonlösung wurde einer Destillation unterworfen, um den Abfall vom Aceton zu befreien. Das Aceton wurde wieder eingesetzt.The resulting acetone solution was subjected to distillation to remove acetone from the waste. The acetone was used again.

Beispiel 5Example 5

Die Abfälle aus den Beispielen 1, 2, 3 und 4 wurden als Zuschlagsstoffe im Konzentrationsbereich 0,5 bis 5 Gew.% (bezogen auf Bitumen) zur Asphaltmodifizierung eingesetzt.The wastes from Examples 1, 2, 3 and 4 were used as additives in the concentration range 0.5 to 5% by weight (based on bitumen) for asphalt modification.

Anstelle der Verfahrensstufe (4) bzw. (8) kann eine an sich bekannte Dünnschichtverdampfung erfolgen. Ebenso kann im Anschluß an die Behandlung mit dispergiertem Natrium die erhaltene Ölphase statt der Verfahrensstufe (4) der Dünnschichtverdampfung unterworfen werden.Instead of process stage (4) or (8), thin-film evaporation known per se can be carried out. Likewise, following the treatment with dispersed sodium, the oil phase obtained can be subjected to thin-film evaporation instead of process step (4).

Das erfindungsgemäße Verfahren zeichnet sich gegenüber den Verfahren des Standes der Technik durch zahlreiche Vorteile aus:

  • hohe Wirtschaftlichkeit
  • hohe Betriebssicherheit
  • mildes Behandlungsverfahren
  • Ermöglichung der dezentralen Entsorgung
  • Teilintegration in vorhandene Anlagen und Verfahren
  • Rückstände des Verfahrens entweder als Zuschlags-/Wertstoffe vollständig wieder einsetzbar für andere Produkte bzw. rückführbar in vorherige Verfahrensstufen.
The process according to the invention is distinguished by numerous advantages over the processes of the prior art:
  • High profitability
  • high operational reliability
  • mild treatment procedure
  • Enabling decentralized disposal
  • Partial integration in existing systems and processes
  • Process residues can either be used as aggregates or recyclable materials for other products or can be traced back to previous process stages.

Das gewonnene Grundöl zeichnete sich durch einen günstigeren und höheren Viskositätsindex als das Frischöl aus. Alle aschebildenden Additive - sonst Verursacher von Schlammbildung (insbesondere im Motor) - werden entfernt, d.h. das gewonnene Grundöl weist einen Aschegehalt von nahezu 0,0 Gew.% auf. Schließlich bleiben die Additive zur Viskositätsverbesserung weitgehend erhalten, und zwar nach bisherigen Ergebnissen zumindest etwa zu einem Drittel des Gehalts des Frischadditivpackage an diesen Additiven.The base oil obtained was characterized by a cheaper and higher viscosity index than the fresh oil. All ash-forming additives - otherwise causing sludge formation (especially in the engine) - are removed, ie the base oil obtained has an ash content of almost 0.0% by weight. Finally, the additives to improve the viscosity are largely retained, in accordance with previous ones Results at least about a third of the content of the fresh additive package in these additives.

Claims (11)

  1. A process for refining and regenerating used oils based on mineral oils by filtering, thermal treatment and stripping of the light ends consisting of solvent and water;
    characterised in that
    used oils after coarse filtering
    (1) are heated to a temperature of 50 to 100°C in a closed mixer and under vigorous stirring there are added thereto - respectively based on the used oil - 0.5 to 2.5 wt.% of an aqueous solution of alkali water glass having a water content of 30 to 70 wt.%, based on the solution, and 0.25 to 2.5 wt.% of an aqueous solution of a polyalkylene glycol represented by the formula
    Figure imgb0008
     in which R = n-alkyl having 8 to 20 carbon atoms, R₁ = hydrogen, alkyl having 1 to 3 carbon atoms, n = 20 to 125, with an average molecular weight of from 1,000 to 10,000 and a water content of from 80 to 97.5 wt.%, based on the solution,
    (2) the obtained mixture is left to settle in a decanter at a temperature of from 70 to 90°C, the settlings are separated and
    (3) the light ends consisting of water and solvent are separated from the oil phase at a temperature of from 100 to 140°C and a pressure of from 2.7 kPa to 13.3 kPa (20 to 100 Torr).
  2. The process claimed in claim 1, characterised in that in process stage (1) heating is effected in a closed mixer to a temperature of from 60 to 80°C and under vigorous stirring there are added - respectively based on the used oil - 0.5 to 2.5 wt.% of an aqueous solution of alkali water glass having a water content of 30 to 70 wt.%, based on the solution, and 0.25 to 2.5 wt.% of an aqueous solution of a polyalkylene glycol represented by the formula
    Figure imgb0009
     in which R₂ = n-alkyl having 10 to 14 carbon atoms, n = 21 to 30 with an average molecular weight of from 2,000 to 5,000 and a water content of from 80 to 97.5 wt.%, based on the solution.
  3. The process claimed in claim 1 or claim 2, characterised in that the oil phase which has been pretreated by the process stages (1) -to (3) is further treated by
    (4) adding to the oil phase at a temperature of from 30 to 120°C 3 to 8 parts by weight of n-alkanes having 6 to 10 carbon atoms per 1 part by weight of the pretreated oil phase, vigorously stirring for some time while maintaining the temperature, leaving the obtained mixture to settle in a decanter at room temperature, removing the settlings, treating the oil phase in an adsorber with a filter unit, said filter unit comprising clays or compacted aluminium oxide, and
    (5) separating the light ends from the obtained oil filtrate at a temperature of from 50 to 80°C and a pressure of from 2.7 to 13.3 kPa (20 to 100 Torr).
  4. Process for treating used oils containing polychlorinated bi- and terphenyls, characterised in that the oil phase pretreated by the process stages (1) to (3) is further treated by
    (6) heating the pretreated used oil phase to a temperature of from 70 to 120°C in a closed mixer and adding thereto 3 to 8 parts by weight of n-alkanes having 6 to 10 carbon atoms per 1 part by weight of the pretreated used oil phase, under vigorous stirring adding thereto, respectively based on the pretreated used oil phase, 0.1 to 0.5 wt.% of an aqueous solution of alkali water glass at pH = 9 and 0.1 to 0.5 wt.% of polyalkylene glycol represented by the general formula
    Figure imgb0010
     in which R₃ = hydrocarbon or methyl, n = 0 to 22, with a hydroxyl number of 100 to 300 mg of KOH/g as specified by DIN 53240 and an average molecular weight of from 380 to 1,050, vigorously stirring for 15 to 120 minutes while maintaining the temperature, adding 0.1 to 0.25 wt.% of anhydrous alkali metasilicate, based on the used oil phase, stirring again for 5 to 15 minutes,
    (7) leaving the obtained mixture to settle in a decanter at room temperature, removing the settlings,
    (8) treating the oil phase at a temperature of from 30 to 60°C in an adsorber with filter unit, said filter unit comprising clays or compacted aluminium oxide, and
    (9) stripping the light ends from the oil filtrate at a temperature of from 50 to 80°C and a pressure of 2.7 to 13.3 kPa (20 to 100 Torr).
  5. The process claimed in claim 4, characterised in that in process stage (6) there is used, based on the used oil phase, 0.1 to 0.5 wt.% of polyethylene glycol represented by the general formula

            HO-(CH ₂ - CH ₂ -O) n -H   IV,

    in which n = 9 to 22, with a hydroxyl number of 100 to 300 mg of KOH/g and an average molecular weight of from 380 to 1,050.
  6. The process claimed in any of the preceding claims, characterised in that the treated oil phase is finally subjected to vacuum distillation at a temperatures of from 200 to 300°C and a pressure of from 0.13 to 6.67 kPa (1 to 50 Torr).
  7. The process claimed in any of the claims 1 to 3, characterised in that subsequent to process stage (3) the pretreated dry oil phase is treated as known per se with finely dispersed sodium by blending in a reactor at a temperature of from 100 to 250°C the oil phase with a sodium/oil dispersion comprising finely dispersed sodium particles in a base oil, removing the formed oil-containing solids, subjecting the oil phase to the treatment according to process stage (4), and finally carrying out distillation.
  8. The process claimed in any of the claims 2 to 7, characterised in that the process stages (4) and (5) are replaced by thin-film evaporation.
  9. The process claimed in any of the claims 1 to 5, characterised in that subsequent to process stage (3) hydrogenation is carried out in the presence of a hydrogenating catalyst, especially at a temperature of from 200 to 400°C and a pressure of from 10·10⁵ Pa to 200·10⁵ Pa (10 to 200 bar), and preferentially at a temperature of from 300 to 380°C and a pressure of from 40·10⁵ Pa to 60·10⁵ Pa (40 to 60 bar), and subsequently distillation is carried out.
  10. The process claimed in any of the preceding claims, characterised in that in process stage (1) the solution of alkali water glass and/or the solution of polyalkylene glycol is used in preheated state, especially preheated to 30 to 60°C, preferentially preheated to about 50°C.
  11. The process as claimed in any of the preceding claims, characterised in that process stage (3) is carried out prior to process stage (2), in which initially the light ends are separated from the obtained mixture, whereafter settling in a decanter is allowed and finally the settlings are removed.
EP88907226A 1987-08-19 1988-08-18 Process for purifying and regenerating used oils Expired - Lifetime EP0377606B1 (en)

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DE3876245D1 (en) 1993-01-07
EP0377606A1 (en) 1990-07-18
AU2269788A (en) 1989-03-09
CN1045122A (en) 1990-09-05
DE3890632D2 (en) 1990-07-19
JPH02504523A (en) 1990-12-20
CN1021233C (en) 1993-06-16
US5141628A (en) 1992-08-25
RU1834902C (en) 1993-08-15
WO1989001508A1 (en) 1989-02-23

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