EP3404084B1 - Washing method for rolling and dressing oils - Google Patents

Washing method for rolling and dressing oils Download PDF

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Publication number
EP3404084B1
EP3404084B1 EP18171973.3A EP18171973A EP3404084B1 EP 3404084 B1 EP3404084 B1 EP 3404084B1 EP 18171973 A EP18171973 A EP 18171973A EP 3404084 B1 EP3404084 B1 EP 3404084B1
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European Patent Office
Prior art keywords
oil
rolling
phase
aluminum
aqueous
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EP18171973.3A
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German (de)
French (fr)
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EP3404084C0 (en
EP3404084A1 (en
Inventor
Olaf Güssgen
Thomas Graf
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Speira GmbH
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Speira GmbH
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/005Working-up used lubricants to recover useful products ; Cleaning using extraction processes; apparatus therefor
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/02Working-up used lubricants to recover useful products ; Cleaning mineral-oil based
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum

Definitions

  • the invention relates to a method for reprocessing oil contaminated with aluminum from rolling/skin-passing processes.
  • Rolling oils and skin-pass oils are cooling lubricants that have a major impact on the cost-effectiveness of production and the quality of the products.
  • the coefficient of friction between the work roll and the rolling stock should be neither too high nor too low.
  • a low coefficient of friction improves lubrication in the roll gap, so that energy consumption, frictional heat and roll wear are reduced.
  • the texture of the skin-pass roll is transferred to the surface of the strip to be rolled and a skin-pass oil is applied beforehand, which leads to a reduction in the forming forces acting in the roll gap of the skin-pass mill stand.
  • the forming forces effective in the roll gap are to be set as precisely as possible in order to maintain the low degrees of forming required during skin-passing just as precisely.
  • both the surfaces of the rolled strips and the surfaces of the work rolls used for their forming are protected.
  • the rolling oils are heavily contaminated by metal abrasion.
  • the impurities are essentially metal abrasion and metal soaps from the rolling stock, for example aluminum and magnesium, as well as metal abrasion from the rollers (e.g. iron and chrome).
  • Comparatively small amounts of rolling oil are used in temper rolling, but these are heavily contaminated with metal abrasion after a short time.
  • the proportion of aluminum in the rolling oil can then be up to 2% by weight and more, based on the mass of the oil.
  • the condition of the rolling oil must be continuously checked during rolling or skin-passing so that the limit concentrations of aluminum for the respective rolling process are not exceeded.
  • high amounts of aluminum in the rolling oil during rolling lead to product quality problems.
  • High levels of metal abrasion in the rolling oil lead to damage to the rolls and the formation of visually conspicuous surface contamination on the rolling stock, such as indentations, dark streaks and holes.
  • the DE 15 45 299 A1 proposes coagulating waste materials from waste oil from motor vehicle engines and transmissions by mixing it with an aqueous alkali metal hydroxide solution with a concentration of 10 to 50% by weight in a proportion of 2 to 15% by weight, based on the mass of the used oil and separating the clarified oil from the coagulation liquid and the suspension of aging products and then processing it using petroleum industry processes, for example refining.
  • the particle sizes are so small and the particle size distribution of the abraded metal is so unfavorable that satisfactory separation from the oil by filtration can hardly be achieved.
  • the U.S. 2,902,439 describes a process for the purification of lubricants from aluminum processing.
  • the lubricant is mixed with an aqueous cleaning solution.
  • This essentially contains sodium aluminate and at least an equal amount by weight of sodium hydroxide. Mixing with the lubricant occurs at a temperature of 120°F (48.9°C) to 210°F (98.9°C).
  • This document also states that only 20 ml of the cleaning solution is sufficient to clean one liter of dirty oil.
  • the U.S. 2,902,439 makes it clear that the treatment of aluminum fines in oil with caustic soda is dangerous because highly explosive hydrogen gas is evolved. Large amounts of caustic soda also produce foam, which is said to be difficult to control.
  • the invention is therefore based on the object of providing a process for the purification and reuse of used rolling oil or skin-pass oil that avoids the aforementioned disadvantages.
  • This problem is solved by a process for recycling oil contaminated with aluminum from rolling or skin-passing processes, in which rolling oil or skin-passing oil contaminated with aluminum is mixed with an aqueous alkali metal hydroxide solution, a phase separation is brought about between the aqueous phase and the oil phase, and then the aqueous phase is the oil phase is separated and the oil phase is freed from residual water and any suspended matter present using a drying agent, the mass ratio of contaminated oil to aqueous alkali metal hydroxide solution being 1 to at least 2.
  • the process according to the invention enables the cleaned oil to be reused as rolling or skin-pass oil.
  • the product oil of the process according to the invention is of high quality. Impurities from thermal treatment of the oil are not present at the time of recycling.
  • the method according to the invention makes it possible to save a great deal of oil in industrial rolling and skin-passing plants.
  • contaminated oils from rolling/skin-passing processes can be cleaned in a discontinuous process without waste-generating filtration and/or thermal separation processes such as distillation or rectification and used again as pure oil.
  • Wastewater that is easy to treat is produced in comparatively small quantities.
  • the aluminum hydroxide obtained can be used in water treatment. Critical waste is avoided.
  • the ecological footprint is significantly lower than in conventional cleaning processes. The same applies to the investment and operating costs.
  • Rolling oils and skin-pass oils within the meaning of the invention are oils and oil-containing liquids intended for rolling and skin-passing.
  • oil for the purposes of the invention includes fatty alcohols, fatty acids, fatty acid esters and kerosene cuts, mineral oils, vegetable oils and synthetic oils and mixtures thereof.
  • the hydrocarbon chains of these compounds can have, for example, 8 to 20, preferably 10 to 18, carbon atoms.
  • the end of the boiling point of the organic chemical compounds mentioned above should be below the lowest annealing temperature of around 320 °C that is customary in the aluminum industry.
  • the kinematic viscosity of the rolling and skin-passing oils at 40° C. is usually below 10 mm 2 /s, preferably below 6 mm 2 /s.
  • Rolling oils and skin-pass oils can also contain standard rolling additives.
  • the oils to be purified as starting material in the process according to the invention have previously been used in skin-passing and rolling of aluminum foils and wires. Compared to when they were first used, these oils are heavily contaminated by metallic abrasion.
  • the impurities contained therein are, for example, aluminum abrasion and other metal abrasion.
  • the proportion of aluminum particles in the contaminated oil can be, for example, 500 to 4000 mg/l. High concentrations of metal abrasion can occur in rolling processes, especially in the Production of very thin strips that greatly affect product quality.
  • the degree of contamination of the oil with metal debris can be determined visually during the rolling or skin-passing process and can also be determined gravimetrically by determining the turbidity or by testing with particle counters and particle size analyzers.
  • the contaminated oil described above is mixed with a dilute aqueous alkali metal hydroxide solution with stirring.
  • the amount of washing liquid is determined by the degree of contamination of the oil with aluminum particles.
  • the mass of the aqueous alkali metal hydroxide solution used is generally at least twice the mass of the contaminated oil.
  • the contaminated oil is introduced into the aqueous alkali metal hydroxide solution.
  • Alkali metal hydroxide solution within the meaning of the invention means a solution of alkaline earth metal hydroxide and/or alkali metal hydroxide.
  • particularly suitable alkali metal hydroxides are sodium hydroxide and potassium hydroxide.
  • the concentration of the alkali metal hydroxide in the aqueous solution is preferably high enough to completely solubilize the aluminum present in the oil.
  • the amount of alkali metal hydroxide that is preferably introduced is such that there is an excess of alkali metal hydroxide compared to the aluminum particles and other metal particles present in the oil.
  • the alkali metal hydroxide solution can contain alkali metal in a concentration of preferably 1 to 9% by weight, particularly preferably 2 to 7% by weight, based on the mass of the solution.
  • the alkali metal hydroxide solution can, for example, have a concentration of 2 to 5% by weight alkali metal hydroxide, based on the mass of the alkali metal hydroxide solution.
  • the volumetric fraction of the aqueous alkali metal hydroxide solution may preferably be greater than 40% v/v based on the volume of rolling oil and aqueous alkali metal hydroxide solution.
  • the aqueous alkali metal hydroxide solution and the contaminated oil are thoroughly mixed.
  • the intensive mixing of the aqueous alkali metal hydroxide solution with the oil washes out the aluminum from the oil phase.
  • Aluminum is thereby converted to aluminum hydroxide and further to aluminate, which are soluble in the alkaline aqueous phase.
  • soaps can also form.
  • the aluminate also remains in solution in the alkaline aqueous phase. Any other metals present also go into solution as hydroxides.
  • a water-soluble polyalkylene glycol can be added to improve the phase separation at the phase interface between the aqueous and oily phases.
  • a polyalkylene glycol is used that is completely soluble in water at 20 °C in any mixing ratio without phase separation.
  • the addition of a polyalkylene glycol for phase separation is particularly useful when the rolling oil contains additives such as acids. These acids can be fatty acids containing from 12 to 16 carbon atoms.
  • the polyalkylene glycol is preferably one of viscosity class 140.
  • the kinematic viscosity of the polyalkylene glycol can be 140 mm 2 /s to 160 mm 2 /s, preferably around 150 mm 2 /s.
  • the kinematic viscosity was determined using a rotational viscometer according to ASTM D-7042.
  • the polyalkylene glycol contains ethylene and propylene units. It can be used in an amount of 1 to 10% by weight, preferably 3 to 6% by weight, based on the mass of alkali metal hydroxide solution and polyalkylene glycol. Surprisingly, it has been shown that water-soluble polyalkylene glycol improves the processing of oils that are present together with acidic additives.
  • the mixing of contaminated oil and aqueous alkali metal hydroxide solution can preferably be carried out in a reactor equipped with a stirrer at room temperature (about 20 °C). There is no heating of the resulting mixture of contaminated oil and aqueous alkali metal hydroxide solution to a temperature of 45 °C or more.
  • the process according to the invention can be carried out at a temperature of 15° C. to 30° C. or even higher. Preferably the process temperature is from 15°C to 25°C.
  • the reactor may preferably be a bottom-conical reactor.
  • Conventional stirrers can be used as the stirrer.
  • an axial stirrer (propeller stirrer) is particularly suitable for enabling intensive mixing of aluminum-containing oil phase and aqueous alkali metal hydroxide phase in the reactor.
  • a tangential stirrer (anchor stirrer) is also conceivable.
  • the reactor is vented. The purpose of venting the reactor is to avoid an increase in hydrogen gas concentration during aluminum scrubbing.
  • the oil is preferably mixed with the aqueous alkali metal hydroxide solution until the oil phase is free of metallic aluminum. However, it is not essential that the oil phase is completely free of metallic aluminum. Intensive mixing of the two phases can take, for example, 30 to 120 minutes, depending on the size of the reactor and the intensity of stirring. A visual inspection is sufficient for this. Before cleaning, the oil is dark and not transparent, after cleaning it is clear and transparent. After cleaning, the oil has a water-clear to yellowish color.
  • the liquid is then left in the reactor until phase separation into an aqueous phase and an oil phase has taken place. Depending on the volume of liquid, this may take 30 to 120 minutes.
  • the aqueous phase with higher density settles in the lower part of the reactor.
  • the lower density, de-aluminum oil floats on top of the aqueous phase.
  • the extent of phase separation or the progress of separation of the two phases can be monitored during the separation process by measuring the electrical Conductivity of the liquid in the reactor or visually.
  • the aqueous phase is separated off. This is done, for example, by allowing the aqueous phase containing aluminate/aluminum hydroxide, which may contain other metal hydroxides, to flow off from the lower part of the reactor.
  • water or an aqueous liquid can be supplied in order to allow the cleaned rolling oil to flow off by the rise in the liquid level in the upper part of the reactor.
  • the oil phase is washed once or twice more with deionized water. During washing, too, the oil is intensively mixed with the water used for washing. A phase separation of the oil phase and the washing water phase is then allowed in turn. Thereafter, the washing water is separated off as before, the aqueous alkaline aluminate-containing phase.
  • the duration of the mixing of the oil and washing water and the duration of the phase separation can be selected in exactly the same way as when washing with and separating off metal hydroxide solution.
  • the purified oil is removed from the reactor.
  • the oil will usually be saturated or nearly saturated with water after the aluminum has been washed away.
  • the proportion of water in the oil can be around 100 ppm.
  • the oil is fed through a filter device.
  • This filter device serves to dry the oil. It also serves to remove any suspended matter still present in the oil.
  • the filter device can contain one or more substances for chemically or physically binding water. Such substances or desiccants include, for example, silica gels, molecular sieves, sodium sulfate, and magnesium sulfate. Sodium sulfate is particularly preferred.
  • the filter device can be designed as a so-called candle filter be filled with the substance for chemically or physically binding water (desiccant). By drying the oil, both water and suspended matter, if any are still present in the oil, are separated from the oil. The oil obtained is essentially anhydrous. This means that the water saturation in the oil is between 20 and 70% of the highest possible water saturation, preferably around 50% or less.
  • the water saturation in the oil can be determined with a capacitive water sensor or by titration according to Karl Fischer.
  • the product oil of the process according to the invention is almost free of metal abrasion. Oil cleanliness can be determined by measuring turbidity.
  • the oil obtained in this way can be reused as pure oil in skin-passing or rolling processes.
  • the aqueous phase containing dissolved aluminum can be neutralized.
  • the neutralization can take place, for example, by adding sulfuric acid.
  • Aluminum hydroxide and, if appropriate, other metal hydroxides are precipitated in the process. During the precipitation of aluminum hydroxide, suspended matter and the remaining oil are trapped, precipitated and separated from the water. After separation of water and solid phase, the water obtained in this way can often be discharged into the sewage system without further treatment, but in accordance with the requirements for direct dischargers.
  • the aluminum can also be washed out of the oil in two reactors connected in parallel in so-called pendulum batch operation, or different process stages of the process according to the invention can be carried out in parallel in both reactors.
  • the process of the invention can be carried out at ambient temperature. No supply of energy in the form of heat is required.
  • the process can be carried out batchwise or continuously.
  • the skin-passing of aluminum sheet in a skin-pass rolling stand 1 takes place with the addition of a skin-pass oil as a cooling lubricant (8 to 10 l/min).
  • a skin-pass oil as a cooling lubricant (8 to 10 l/min).
  • the skin-pass oil is conveyed from a pure oil tank 1 to the skin-pass mill stand 1 .
  • the used skin-passing oil enriched with aluminum is transferred via the line 3 into the accumulation tank 4 for contaminated skin-passing oil.
  • the contaminated oil is fed into the reactor 7 through line 5 .
  • Reactor 7 is equipped with a propeller stirrer 8 and a pressure aerator 9.
  • the enrichment of hydrogen gas in the reactor 7 is to be avoided by the pressurized aerator 9 .
  • dilute alkali metal hydroxide solution is introduced into reactor 7 in about a 10-fold stoichiometric excess, based on aluminum, as 2 to 3% sodium hydroxide solution before contaminated oil is fed into the reactor via line 5 to wash out the aluminum particles.
  • the dilute alkali metal hydroxide solution can also be fed into the reactor 7 via the lines 5 and 6 .
  • Alkali metal hydroxide can be stored in a storage tank 10 as a more concentrated solution.
  • liquid alkali metal hydroxide solution is transferred from storage tank 10 via line 11 into a mixer and brought to the desired concentration there by adding water from source 14 via line 13 .
  • the used rolling oil contaminated with aluminum is intensively mixed with the alkali metal hydroxide solution using the propeller stirrer 8.
  • the metal aluminum is to be largely converted into aluminum hydroxide.
  • a phase separation of the aqueous alkaline phase and the oil phase is then brought about in the reactor 7 .
  • the extent of phase separation is determined by measuring the electrical conductivity. If the phase separation in the reactor is largely complete, the aqueous alkaline phase is drained off at the bottom of the reactor and conducted via line 19 for further treatment 20 such as neutralization.
  • the oil phase is then drained from the reactor 7 and fed to a candle filter 16 via line 15 .
  • the oil is dried in the candle filter 16 . Furthermore, suspended matter is retained in the filter material as it flows through the filter 16 .
  • the oil flowing out of the filter is fed to the clean oil tank 1 via line 17 directed. From there it can be fed back to skin-pass mill 2 for use in a skin-pass process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

TECHNISCHES GEBIET DER ERFINDUNGTECHNICAL FIELD OF THE INVENTION

Die Erfindung betrifft ein Verfahren zur Wiederaufbereitung von mit Aluminium verunreinigtem Öl aus Walz-/Dressier-Prozessen.The invention relates to a method for reprocessing oil contaminated with aluminum from rolling/skin-passing processes.

HINTERGRUND DER ERFINDUNGBACKGROUND OF THE INVENTION

Walzöle und Dressieröle sind Kühlschmierstoffe, die einen großen Einfluss auf die Wirtschaftlichkeit der Produktion und die Qualität der Erzeugnisse haben. Beim Walzen und beim Dressieren soll der Reibwert zwischen Arbeitswalze und Walzgut weder zu hoch noch zu niedrig sein. Ein niedriger Reibwert verbessert die Schmierung im Walzspalt, so dass Energieaufwand, Reibungswärme und Walzenverschleiß verringert werden.Rolling oils and skin-pass oils are cooling lubricants that have a major impact on the cost-effectiveness of production and the quality of the products. During rolling and skin-passing, the coefficient of friction between the work roll and the rolling stock should be neither too high nor too low. A low coefficient of friction improves lubrication in the roll gap, so that energy consumption, frictional heat and roll wear are reduced.

Beim Dressieren von Aluminiumbändern wird die Textur der Dressierwalze auf die Oberfläche des jeweils zu walzenden Bandes übertragen und zuvor ein Dressieröl aufgebracht, das zu einer Minderung der im Walzspalt des Dressierwalzgerüstes wirkenden Umformkräfte führt. Auf diese Weise soll eine möglichst exakte Einstellung der im Walzspalt jeweils wirksamen Umformkräfte erreicht werden, um die beim Dressieren geforderten geringen Umformgrade ebenso exakt einzuhalten. Gleichzeitig werden aufgrund der Benetzung mit Walzölflüssigkeit sowohl die Oberflächen der gewalzten Bänder als auch die Oberflächen der zu ihrer Umformung eingesetzten Arbeitswalzen geschont.When skin-passing aluminum strips, the texture of the skin-pass roll is transferred to the surface of the strip to be rolled and a skin-pass oil is applied beforehand, which leads to a reduction in the forming forces acting in the roll gap of the skin-pass mill stand. In this way, the forming forces effective in the roll gap are to be set as precisely as possible in order to maintain the low degrees of forming required during skin-passing just as precisely. At the same time, due to the wetting with rolling oil liquid, both the surfaces of the rolled strips and the surfaces of the work rolls used for their forming are protected.

Nach einer Reihe von Walzvorgängen sind die Walzöle durch Metallabrieb stark verunreinigt. Bei den Verunreinigungen handelt es sich im Wesentlichen um Metallabrieb und Metallseifen aus dem Walzgut, beispielsweise Aluminium und Magnesium, sowie um Metallabrieb aus den Walzen (beispielweise Eisen und Chrom). Beim Dressierwalzen kommen vergleichsweise geringe Mengen von Walzöl zum Einsatz, die jedoch nach kurzer Zeit mit Metallabrieb stark verunreinigt sind. Der Anteil an Aluminium im Walzöl kann dann bis zu 2 Gew.-% und mehr, bezogen auf die Masse des Öls, betragen.After a series of rolling processes, the rolling oils are heavily contaminated by metal abrasion. The impurities are essentially metal abrasion and metal soaps from the rolling stock, for example aluminum and magnesium, as well as metal abrasion from the rollers (e.g. iron and chrome). Comparatively small amounts of rolling oil are used in temper rolling, but these are heavily contaminated with metal abrasion after a short time. The proportion of aluminum in the rolling oil can then be up to 2% by weight and more, based on the mass of the oil.

Der Zustand des Walzöls muss während des Walzens oder Dressierens laufend kontrolliert werden, damit die Grenzkonzentrationen an Aluminium für die jeweiligen Walzverfahren nicht überschritten werden. Insbesondere bei sehr dünnen Folien und Blechen führen hohe Aluminiummengen im Walzöl beim Walzen zu Problemen mit der Produktqualität. Hohe Mengen an Metallabrieb im Walzöl führen zu Beschädigungen an den Walzen und zur Bildung von visuell auffälligen Oberflächenkontaminationen auf dem Walzgut, wie Einwalzungen, dunklen Streifen und Löchern.The condition of the rolling oil must be continuously checked during rolling or skin-passing so that the limit concentrations of aluminum for the respective rolling process are not exceeded. In the case of very thin foils and sheets in particular, high amounts of aluminum in the rolling oil during rolling lead to product quality problems. High levels of metal abrasion in the rolling oil lead to damage to the rolls and the formation of visually conspicuous surface contamination on the rolling stock, such as indentations, dark streaks and holes.

Damit Walzöle länger gebrauchsfähig bleiben, werden sie bisher durch Anschwemmfiltration über Plattenfilter gereinigt. Nachteilig daran ist, dass eine große Menge Öl durch Filterhilfsmittel ausgetragen wird. Zu berücksichtigen ist in diesem Zusammenhang auch, dass Aluminium enthaltende Rückstände zur Selbstentzündlichkeit neigen. Besondere Vorkehrungen müssten daher für eine sichere Lagerung oder den sicheren Transport für die Aluminium enthaltenden Rückstände getroffen werden. Darüber hinaus fallen große Abfallmengen wegen der gebrauchten Filterhilfsmittel und der gebrauchten Filtervliese an. Das gleiche gilt für eine Filtration des verunreinigten Öls über Rückspülfilter.So that rolling oils remain usable for longer, they have been cleaned by precoat filtration using plate filters. The disadvantage of this is that a large amount of oil is discharged through filter aids. In this context, it must also be taken into account that residues containing aluminum tend to self-ignite. Special precautions would therefore have to be taken for safe storage or transport for the aluminum-containing residues. In addition, large amounts of waste arise because of the used filter aids and the used filter fleece. The same applies to filtration of the contaminated oil using a backwash filter.

Man könnte darüber hinaus an destillative Verfahren zur Abtrennung des Öls von den verunreinigenden Feststoffen denken. Auch hier sind die Investitionskosten hoch. Der Energieaufwand ist ebenfalls hoch und durch die thermische Beanspruchung des Öls kann dessen Qualität sinken, weil sich im Öl bei der Destillation Crackprodukte bilden können. Zentrifugale Trennverfahren haben eine unzureichende Partikelabscheiderate bei kleinen Partikeldurchmessern. Für Flockungsverfahren ist ein hoher Energieaufwand erforderlich, und das Gefahrenpotential des ölhaltigen Metallschlamms ist hoch. Darüber hinaus ist der für ein Flockungsverfahren erforderliche Arbeitsaufwand wegen des aufwendigen Handlings des Abfalls groß. Ein solches Verfahren ist beispielsweise in der DE 26 13 878 C2 beschrieben, wo vorgeschlagen wird, Walzöle mit Natriumcarbonatlösung zu koagulieren und das gebildete Koagulat abzuzentrifugieren.One could also think of distillative processes to separate the oil from the contaminating solids. Here, too, the investment costs are high. The energy input is also high and the thermal stress on the oil can reduce its quality because cracked products can form in the oil during distillation. Centrifugal separation processes have an insufficient particle separation rate for small particle diameters. A large amount of energy is required for flocculation processes and the hazard potential of the oily metal sludge is high. In addition, the amount of work required for a flocculation process due to the complex handling of the waste. Such a method is, for example, in DE 26 13 878 C2 described where it is proposed to coagulate rolling oils with sodium carbonate solution and to centrifuge off the coagulum formed.

Die DE 15 45 299 A1 schlägt vor, Abfallstoffe aus Altöl aus Motoren und Getrieben von Kraftfahrzeugen durch Vermischen mit einer wässrigen Alkalihydroxid-Lösung einer Konzentration von 10 bis 50 Gew.-% im Mengenverhältnis von 2 bis 15 Gew.-%, bezogen auf die Masse des Altöls, zu koagulieren und das geklärte Öl von der Koagulationsflüssigkeit und der Suspension der Alterungsprodukte abzutrennen und anschließend mit den Verfahren der Erdölindustrie weiterzuverarbeiten, beispielsweise durch Raffinieren.The DE 15 45 299 A1 proposes coagulating waste materials from waste oil from motor vehicle engines and transmissions by mixing it with an aqueous alkali metal hydroxide solution with a concentration of 10 to 50% by weight in a proportion of 2 to 15% by weight, based on the mass of the used oil and separating the clarified oil from the coagulation liquid and the suspension of aging products and then processing it using petroleum industry processes, for example refining.

In gebrauchten Dressierölen sind die Teilchengrößen so niedrig und die Teilchengrößenverteilung des Metallabriebs ist so ungünstig, dass eine zufriedenstellende Abtrennung aus dem Öl durch Filtration kaum erreichbar ist.In used skin-pass oils, the particle sizes are so small and the particle size distribution of the abraded metal is so unfavorable that satisfactory separation from the oil by filtration can hardly be achieved.

Die US 2 902 439 beschreibt ein Verfahren zur Aufreinigung von Schmierstoffen aus der Aluminiumverarbeitung. In diesem Verfahren wird das Schmiermittel mit einer wässrigen Cleaning-Lösung vermischt. Diese enthält im Wesentlichen Natriumaluminat und wenigstens eine gleiche Gewichtsmenge Natriumhydroxid. Das Vermischen mit dem Schmiermittel erfolgt bei einer Temperatur von 120 °F (48,9°C) bis 210 °F (98,9 °C). Dieses Dokument führt ferner aus, dass nur 20 ml der Reinigungslösung ausreichen, um einen Liter verschmutztes Öl zu reinigen. Die US 2 902 439 macht deutlich, dass die Behandlung von Aluminiumfeinteilen in Öl mit Natronlauge gefährlich ist, weil sich hochexplosives Wasserstoffgas entwickelt. Ferner entwickelt sich durch größere Mengen Natronlauge Schaum, der schwer zu beherrschen sein soll. Um das Verfahren beherrschbar zu gestalten und um die Bildung von Wasserstoffgas und Schaum zu verringern oder zu unterdrücken, wird gemäß der US 2 902 439 der Zusatz von Natriumaluminat vorgeschlagen. Weil aber dadurch bei der Aufreinigung des Schmiermittels die Reaktionsgeschwindigkeit von Natronlauge und Aluminiumteilchen stark abgebremst wird, ist im Verfahren der US 2 902 439 die Temperatur erhöht, um eine angemessene Verfahrensdauer einzuhalten. Mit derselben Problematik und einer sehr ähnlichen Lösung beschäftigt sich auch die EP 0 030 805 A1 , in der Natriummetasilicat (Wasserglas) gemeinsam mit Natriumhydroxid angewendet wird. Durch den Einsatz von Natriummetasilicat wird die Natronlauge enthaltende Flüssigkeit sehr zähflüssig und die Reaktionsgeschwindigkeit von Natriumhydroxid und Aluminium wird stark reduziert. Auch in diesem Verfahren wird die Temperatur erhöht, um das durch den Einsatz von Wasserglas abgebremste Verfahren wieder zu beschleunigen.The U.S. 2,902,439 describes a process for the purification of lubricants from aluminum processing. In this process, the lubricant is mixed with an aqueous cleaning solution. This essentially contains sodium aluminate and at least an equal amount by weight of sodium hydroxide. Mixing with the lubricant occurs at a temperature of 120°F (48.9°C) to 210°F (98.9°C). This document also states that only 20 ml of the cleaning solution is sufficient to clean one liter of dirty oil. The U.S. 2,902,439 makes it clear that the treatment of aluminum fines in oil with caustic soda is dangerous because highly explosive hydrogen gas is evolved. Large amounts of caustic soda also produce foam, which is said to be difficult to control. In order to make the process manageable and to reduce or suppress the formation of hydrogen gas and foam, according to U.S. 2,902,439 the addition of sodium aluminate is suggested. But because this reduces the reaction speed of caustic soda and aluminum particles when cleaning the lubricant is strongly decelerated, is in the process of U.S. 2,902,439 increased the temperature to ensure a reasonable length of the procedure. The also deals with the same problem and a very similar solution EP 0 030 805 A1 , in which sodium metasilicate (water glass) is used together with sodium hydroxide. The use of sodium metasilicate makes the liquid containing caustic soda very viscous and the reaction rate of sodium hydroxide and aluminum is greatly reduced. In this process, too, the temperature is increased in order to accelerate the process, which has been slowed down by the use of water glass.

ZUSAMMENFASSUNG DER ERFINDUNGSUMMARY OF THE INVENTION

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Aufreinigung und Wiederverwendung von gebrauchtem Walzöl oder Dressieröl bereitzustellen, das die zuvor genannten Nachteile vermeidet.The invention is therefore based on the object of providing a process for the purification and reuse of used rolling oil or skin-pass oil that avoids the aforementioned disadvantages.

Gelöst wird diese Aufgabe durch ein Verfahren zur Wiederaufbereitung von mit Aluminium verunreinigtem Öl aus Walz- oder Dressier-Prozessen, in dem man mit Aluminium verunreinigtes Walzöl oder Dressieröl mit wässriger Alkalimetallhydroxidlösung vermischt, eine Phasentrennung zwischen wässriger Phase und Ölphase herbeiführt, anschließend die wässrige Phase von der Ölphase abtrennt und die Ölphase mit einem Trocknungsmittel von Restwasser und gegebenenfalls vorhandenen Schwebstoffen befreit, wobei das Massenverhältnis von verunreinigtem Öl zu wässrige Alkalimetallhydroxidlösung 1 zu mindestens 2 beträgt.This problem is solved by a process for recycling oil contaminated with aluminum from rolling or skin-passing processes, in which rolling oil or skin-passing oil contaminated with aluminum is mixed with an aqueous alkali metal hydroxide solution, a phase separation is brought about between the aqueous phase and the oil phase, and then the aqueous phase is the oil phase is separated and the oil phase is freed from residual water and any suspended matter present using a drying agent, the mass ratio of contaminated oil to aqueous alkali metal hydroxide solution being 1 to at least 2.

Das erfindungsgemäße Verfahren ermöglicht die Wiederverwertung des gereinigten Öls als Walz- oder Dressieröl. Das Produktöl des erfindungsgemäßen Verfahrens hat eine hohe Qualität. Verunreinigungen durch thermische Behandlung des Öls sind zum Zeitpunkt der Wiederverwertung nicht vorhanden. Durch das erfindungsgemäße Verfahren wird eine hohe Einsparung an Öl in industriellen Walz- und Dressieranlagen ermöglicht.The process according to the invention enables the cleaned oil to be reused as rolling or skin-pass oil. The product oil of the process according to the invention is of high quality. Impurities from thermal treatment of the oil are not present at the time of recycling. The method according to the invention makes it possible to save a great deal of oil in industrial rolling and skin-passing plants.

Mit dem erfindungsgemäßen Verfahren können verunreinigte Öle aus Walz-/Dressier-Prozessen ohne Abfall erzeugende Filtrationen und/oder thermische Trennverfahren wie Destillation oder Rektifikation in einem diskontinuierlichen Prozess gereinigt und wieder als Reinöl eingesetzt werden. Es entstehen leicht aufzubereitende Abwässer in vergleichsweise geringen Mengen. Das erhaltene Aluminiumhydroxid kann in der Wasseraufbereitung verwendet werden. Kritische Abfälle werden vermieden. Der ökologische Footprint ist deutlich geringer als in herkömmlichen Reinigungsverfahren. Ebenso verhält es sich mit den Investitions- und Betriebskosten.With the method according to the invention, contaminated oils from rolling/skin-passing processes can be cleaned in a discontinuous process without waste-generating filtration and/or thermal separation processes such as distillation or rectification and used again as pure oil. Wastewater that is easy to treat is produced in comparatively small quantities. The aluminum hydroxide obtained can be used in water treatment. Critical waste is avoided. The ecological footprint is significantly lower than in conventional cleaning processes. The same applies to the investment and operating costs.

BESCHREIBUNG DER BEVORZUGTEN AUSFÜHRUNGSFORMENDESCRIPTION OF THE PREFERRED EMBODIMENTS

Walzöle und Dressieröle im Sinne der Erfindung sind Öle und Öl enthaltende Flüssigkeiten, die zum Walzen und Dressieren bestimmt sind. Der Begriff Öl im Sinne der Erfindung umfasst Fettalkohole, Fettsäuren, Fettsäureester und Kerosinschnitte, Mineralöle, Pflanzenöle und synthetische Öle sowie deren Gemische. Die Kohlenwasserstoffketten dieser Verbindungen können beispielsweise 8 bis 20, vorzugsweise 10 bis 18 Kohlenstoffatome aufweisen. Das Siedeende der zuvor genannten organisch chemischen Verbindungen sollte unter der in der Aluminium-Industrie üblichen niedrigsten Glühtemperatur von etwa 320 °C liegen. Die kinematische Viskosität der Walz- und Dressieröle bei 40 °C liegt üblicherweise unter 10 mm2/s, vorzugsweise unter 6 mm2/s. Walzöle und Dressieröle können darüber hinaus übliche Walzadditive enthalten.Rolling oils and skin-pass oils within the meaning of the invention are oils and oil-containing liquids intended for rolling and skin-passing. The term oil for the purposes of the invention includes fatty alcohols, fatty acids, fatty acid esters and kerosene cuts, mineral oils, vegetable oils and synthetic oils and mixtures thereof. The hydrocarbon chains of these compounds can have, for example, 8 to 20, preferably 10 to 18, carbon atoms. The end of the boiling point of the organic chemical compounds mentioned above should be below the lowest annealing temperature of around 320 °C that is customary in the aluminum industry. The kinematic viscosity of the rolling and skin-passing oils at 40° C. is usually below 10 mm 2 /s, preferably below 6 mm 2 /s. Rolling oils and skin-pass oils can also contain standard rolling additives.

Die als Ausgangsmaterial in dem erfindungsgemäßen Verfahren zu reinigenden Öle sind zuvor beim Dressieren und Walzen von Folien und Drähten aus Aluminium eingesetzt worden. Diese Öle sind im Vergleich zu ihrer ersten Verwendung durch metallischen Abrieb stark verunreinigt. Die darin enthaltenen Verunreinigungen sind beispielsweise Aluminiumabrieb und anderer Metallabrieb. Der Anteil an Aluminiumteilchen in dem verunreinigten Öl kann beispielsweise 500 bis 4.000 mg/l betragen. Hohe Konzentrationen an Metallabrieb können in Walzprozessen, insbesondere bei der Herstellung sehr dünner Bänder, die Produktqualität stark beeinträchtigen. Der Verschmutzungsgrad des Öls mit Metallabrieb ist während der Walz- oder Dressierverfahren visuell feststellbar und kann auch gravimetrisch durch Bestimmung der Trübung oder durch Untersuchung mit Partikelzählern und Partikelgrößenanalysatoren bestimmt werden.The oils to be purified as starting material in the process according to the invention have previously been used in skin-passing and rolling of aluminum foils and wires. Compared to when they were first used, these oils are heavily contaminated by metallic abrasion. The impurities contained therein are, for example, aluminum abrasion and other metal abrasion. The proportion of aluminum particles in the contaminated oil can be, for example, 500 to 4000 mg/l. High concentrations of metal abrasion can occur in rolling processes, especially in the Production of very thin strips that greatly affect product quality. The degree of contamination of the oil with metal debris can be determined visually during the rolling or skin-passing process and can also be determined gravimetrically by determining the turbidity or by testing with particle counters and particle size analyzers.

Das zuvor beschriebene verunreinigte Öl wird erfindungsgemäß mit einer verdünnten wässrigen Alkalimetallhydroxidlösung unter Rühren vermischt. Grundsätzlich bestimmt sich die Menge an Waschflüssigkeit nach dem Grad der Verunreinigung des Öls mit Aluminiumteilchen. Im erfindungsgemäßen Verfahren beträgt die Masse der eingesetzten wässrigen Alkalimetallhydroxidlösung in der Regel mindestens die doppelte Masse des verunreinigten Öls.According to the present invention, the contaminated oil described above is mixed with a dilute aqueous alkali metal hydroxide solution with stirring. Basically, the amount of washing liquid is determined by the degree of contamination of the oil with aluminum particles. In the process according to the invention, the mass of the aqueous alkali metal hydroxide solution used is generally at least twice the mass of the contaminated oil.

Vorzugsweise wird das verunreinigte Öl in die wässrige Alkalimetallhydroxidlösung eingebracht. Alkalimetallhydroxidlösung im Sinne der Erfindung bedeutet eine Lösung von Erdalkalimetallhydroxid und/oder Alkalimetallhydroxid. Erfindungsgemäß besonders geeignete Alkalimetallhydroxide sind Natriumhydroxid und Kaliumhydroxid. Die Konzentration des Alkalimetallhydroxids in der wässrigen Lösung ist vorzugsweise so hoch, dass das im Öl vorhandene Aluminium vollständig in Lösung gebracht wird. In der Regel ist die vorzugsweise vorgelegte Menge an Alkalimetallhydroxid so dimensioniert, dass ein Alkalimetallhydroxidüberschuss im Vergleich zu den im Öl befindlichen Aluminiumteilchen und übrigen Metallteilchen vorhanden ist. Die Alkalimetallhydroxidlösung kann erfindungsgemäß Alkalimetall in einer Konzentration von vorzugsweise 1 bis 9 Gew.-%, besonders bevorzugt 2 bis 7 Gew.-%, bezogen auf die Masse der Lösung enthalten. Die vorgelegte Alkalimetallhydroxidlösung kann im erfindungsgemäßen Verfahren beispielsweise eine Konzentration von 2 bis 5 Gew.-% Alkalimetallhydroxid, bezogen auf die Masse der Alkalimetallhydroxidlösung, aufweisen. Der volumetrische Anteil der wässrigen Alkalimetallhydroxidlösung kann vorzugsweise bei mehr als 40% V/V, bezogen auf das Volumen von Walzöl und wässriger Alkalimetallhydroxidlösung liegen.Preferably, the contaminated oil is introduced into the aqueous alkali metal hydroxide solution. Alkali metal hydroxide solution within the meaning of the invention means a solution of alkaline earth metal hydroxide and/or alkali metal hydroxide. According to the invention, particularly suitable alkali metal hydroxides are sodium hydroxide and potassium hydroxide. The concentration of the alkali metal hydroxide in the aqueous solution is preferably high enough to completely solubilize the aluminum present in the oil. As a rule, the amount of alkali metal hydroxide that is preferably introduced is such that there is an excess of alkali metal hydroxide compared to the aluminum particles and other metal particles present in the oil. According to the invention, the alkali metal hydroxide solution can contain alkali metal in a concentration of preferably 1 to 9% by weight, particularly preferably 2 to 7% by weight, based on the mass of the solution. In the process according to the invention, the alkali metal hydroxide solution can, for example, have a concentration of 2 to 5% by weight alkali metal hydroxide, based on the mass of the alkali metal hydroxide solution. The volumetric fraction of the aqueous alkali metal hydroxide solution may preferably be greater than 40% v/v based on the volume of rolling oil and aqueous alkali metal hydroxide solution.

Die wässrige Alkalimetallhydroxidlösung und das verunreinigte Öl werden intensiv durchmischt. Durch das intensive Vermischen der wässrigen Alkalimetallhydroxidlösung mit dem Öl erfolgt ein Auswaschen des Aluminiums aus der Ölphase. Aluminium wird dabei zu Aluminiumhydroxid und weiter zu Aluminat umgesetzt, die in der alkalischen wässrigen Phase löslich sind. In Abhängigkeit von gegebenenfalls im Öl enthaltenen Additiven können sich auch Seifen bilden. Auch das Aluminat bleibt in der alkalischen wässrigen Phase in Lösung. Gegebenenfalls vorhandene andere Metalle gehen auch als Hydroxide in Lösung.The aqueous alkali metal hydroxide solution and the contaminated oil are thoroughly mixed. The intensive mixing of the aqueous alkali metal hydroxide solution with the oil washes out the aluminum from the oil phase. Aluminum is thereby converted to aluminum hydroxide and further to aluminate, which are soluble in the alkaline aqueous phase. Depending on any additives contained in the oil, soaps can also form. The aluminate also remains in solution in the alkaline aqueous phase. Any other metals present also go into solution as hydroxides.

Im erfindungsgemäßen Verfahren wird dem verunreinigten Öl weder ein Gemisch von Natriumhydroxid und Natriumaluminat noch ein Gemisch von Natriumhydroxid und Natriummetasilicat zugesetzt.Neither a mixture of sodium hydroxide and sodium aluminate nor a mixture of sodium hydroxide and sodium metasilicate is added to the contaminated oil in the process of this invention.

Zur Verbesserung der Phasentrennung an der Phasengrenzfläche zwischen wässriger und öliger Phase kann ein wasserlösliches Polyalkylenglykol zugesetzt werden. Zur Anwendung kommt ein Polyalkylenglykol, das in jedem Mischungsverhältnis mit Wasser bei 20 °C vollständig ohne Phasentrennung löslich ist. Der Zusatz eines Polyalkylenglykols zur Phasentrennung ist insbesondere dann sinnvoll, wenn das Walzöl Additive wie Säuren enthält. Diese Säuren können Fettsäuren mit 12 bis 16 Kohlenstoffatomen sein. Das Polyalkylenglykol ist vorzugsweise ein solches der Viskositätsklasse 140. Die kinematische Viskosität des Polyalkylenglykols kann bei 140 mm2/s bis 160 mm2/s, vorzugsweise bei etwa 150 mm2/s liegen. Die kinematische Viskosität wurde mit einem Rotationsviskosimeter gemäß ASTM D-7042 bestimmt. Vorzugsweise enthält das Polyalkylenglykol Ethylen- und Propyleneinheiten. Es kann in einer Menge von 1 bis 10 Gew.-%, vorzugsweise 3 bis 6 Gew.-%, bezogen auf die Masse von Alkalimetallhydroxidlösung und Polyalkylenglykol eingesetzt werden. Überraschend hat sich gezeigt, dass wasserlösliches Polyalkylenglykol die Aufbereitung von Ölen, die gemeinsam mit sauren Additiven vorliegen, verbessert.A water-soluble polyalkylene glycol can be added to improve the phase separation at the phase interface between the aqueous and oily phases. A polyalkylene glycol is used that is completely soluble in water at 20 °C in any mixing ratio without phase separation. The addition of a polyalkylene glycol for phase separation is particularly useful when the rolling oil contains additives such as acids. These acids can be fatty acids containing from 12 to 16 carbon atoms. The polyalkylene glycol is preferably one of viscosity class 140. The kinematic viscosity of the polyalkylene glycol can be 140 mm 2 /s to 160 mm 2 /s, preferably around 150 mm 2 /s. The kinematic viscosity was determined using a rotational viscometer according to ASTM D-7042. Preferably the polyalkylene glycol contains ethylene and propylene units. It can be used in an amount of 1 to 10% by weight, preferably 3 to 6% by weight, based on the mass of alkali metal hydroxide solution and polyalkylene glycol. Surprisingly, it has been shown that water-soluble polyalkylene glycol improves the processing of oils that are present together with acidic additives.

Das Vermischen von verunreinigtem Öl und wässriger Alkalimetallhydroxidlösung kann vorzugsweise in einem mit Rührer ausgerüstetem Reaktor bei Raumtemperatur (etwa 20 °C) erfolgen. Es erfolgt kein Erwärmen der erhaltenen Mischung aus verunreinigtem Öl und wässriger Alkalimetallhydroxidlösung auf eine Temperatur von 45 ° C oder mehr. Das erfindungsgemäße Verfahren kann bei einer Temperatur von 15°C bis 30 °C oder auch darüber durchgeführt werden. Vorzugsweise beträgt die Verfahrenstemperatur 15 °C bis 25°C.The mixing of contaminated oil and aqueous alkali metal hydroxide solution can preferably be carried out in a reactor equipped with a stirrer at room temperature (about 20 °C). There is no heating of the resulting mixture of contaminated oil and aqueous alkali metal hydroxide solution to a temperature of 45 °C or more. The process according to the invention can be carried out at a temperature of 15° C. to 30° C. or even higher. Preferably the process temperature is from 15°C to 25°C.

Der Reaktor kann vorzugsweise ein zum Boden hin konisch gebildeter Reaktor sein. Als Rührwerk können übliche Rührer eingesetzt werden. So ist beispielsweise ein Axialrührer (Propellerrührer) besonders geeignet, in dem Reaktor eine intensive Vermischung von Aluminium enthaltender Ölphase und wässriger Alkalimetallhydroxidphase zu ermöglichen. Denkbar ist auch ein Tangentialrührer (Ankerrührer). Vorzugsweise ist der Reaktor belüftet. Durch die Belüftung des Reaktors soll ein Konzentrationsanstieg von Wasserstoffgas während des Auswaschens des Aluminiums vermieden werden.The reactor may preferably be a bottom-conical reactor. Conventional stirrers can be used as the stirrer. For example, an axial stirrer (propeller stirrer) is particularly suitable for enabling intensive mixing of aluminum-containing oil phase and aqueous alkali metal hydroxide phase in the reactor. A tangential stirrer (anchor stirrer) is also conceivable. Preferably the reactor is vented. The purpose of venting the reactor is to avoid an increase in hydrogen gas concentration during aluminum scrubbing.

Das Durchmischen des Öls mit der wässrigen Alkalimetallhydroxidlösung erfolgt vorzugsweise solange bis die Ölphase frei von metallischem Aluminium ist. Es ist aber nicht zwingend, dass die Ölphase vollständig von metallischem Aluminium befreit ist. Die intensive Durchmischung der beiden Phasen kann je nach Reaktorgröße und Rührintensität beispielsweise 30 bis 120 Minuten dauern. Eine visuelle Sichtkontrolle ist dazu ausreichend. Vor der Reinigung ist das Öl dunkel und nicht transparent, nach der Reinigung klar und transparent. Das Öl weist nach der Reinigung eine wasserklare bis gelbliche Färbung auf.The oil is preferably mixed with the aqueous alkali metal hydroxide solution until the oil phase is free of metallic aluminum. However, it is not essential that the oil phase is completely free of metallic aluminum. Intensive mixing of the two phases can take, for example, 30 to 120 minutes, depending on the size of the reactor and the intensity of stirring. A visual inspection is sufficient for this. Before cleaning, the oil is dark and not transparent, after cleaning it is clear and transparent. After cleaning, the oil has a water-clear to yellowish color.

Anschließend belässt man die Flüssigkeit im Reaktor bis eine Phasentrennung in eine wässrige Phase und eine Ölphase erfolgt ist. Dazu kann in Abhängigkeit vom Flüssigkeitsvolumen eine Zeit von 30 bis 120 Minuten erforderlich sein. Die wässrige Phase mit höherer Dichte lagert sich im unteren Teil des Reaktors ab. Das von Aluminium befreite Öl mit geringerer Dichte schwimmt auf der wässrigen Phase auf. Das Ausmaß der Phasentrennung oder der Fortschritt der Trennung der beiden Phasen kann während des Trennungsprozesses überwacht werden durch Messung der elektrischen Leitfähigkeit der Flüssigkeit im Reaktor oder visuell. Die wässrige Phase wird nach Phasentrennung abgetrennt. Das erfolgt beispielsweise dadurch, dass man die wässrige Aluminat/Aluminiumhydroxid enthaltende Phase, die gegebenenfalls weitere Metallhydroxide enthält, aus dem unteren Teil des Reaktors abfließen lässt. Alternativ kann vorzugsweise im unteren Teil des Reaktors Wasser oder eine wässrige Flüssigkeit zugeführt werden, um so das gereinigte Walzöl durch den Anstieg des Flüssigkeitsspiegels im oberen Teil des Reaktors abfließen zu lassen. Vorteilhaft an dieser Verfahrensführung ist, dass sich eventuell noch vorhandene Schwebstoffe durch ein Gitter leichter zurückhalten lassen.The liquid is then left in the reactor until phase separation into an aqueous phase and an oil phase has taken place. Depending on the volume of liquid, this may take 30 to 120 minutes. The aqueous phase with higher density settles in the lower part of the reactor. The lower density, de-aluminum oil floats on top of the aqueous phase. The extent of phase separation or the progress of separation of the two phases can be monitored during the separation process by measuring the electrical Conductivity of the liquid in the reactor or visually. After phase separation, the aqueous phase is separated off. This is done, for example, by allowing the aqueous phase containing aluminate/aluminum hydroxide, which may contain other metal hydroxides, to flow off from the lower part of the reactor. Alternatively, preferably in the lower part of the reactor, water or an aqueous liquid can be supplied in order to allow the cleaned rolling oil to flow off by the rise in the liquid level in the upper part of the reactor. The advantage of this process is that any suspended matter that may still be present can be held back more easily by a grid.

Gegebenenfalls wird die Ölphase noch einmal oder zweimal mit entsalztem Wasser gewaschen. Auch beim Waschen erfolgt eine intensive Durchmischung des Öls mit dem zum Waschen eingesetzten Wasser. Anschließend lässt man wiederum eine Phasentrennung von Ölphase und Waschwasserphase zu. Danach wird das Waschwasser wie zuvor die wässrige alkalische Aluminat enthaltende Phase abgetrennt. Die Dauer des Durchmischens von Öl und Waschwasser und die Dauer der Phasentrennung können genauso gewählt werden wie beim Waschen mit und Abtrennen von Metallhydroxidlösung.If appropriate, the oil phase is washed once or twice more with deionized water. During washing, too, the oil is intensively mixed with the water used for washing. A phase separation of the oil phase and the washing water phase is then allowed in turn. Thereafter, the washing water is separated off as before, the aqueous alkaline aluminate-containing phase. The duration of the mixing of the oil and washing water and the duration of the phase separation can be selected in exactly the same way as when washing with and separating off metal hydroxide solution.

Nach Abtrennen der wässrigen Metallhydroxidlösung oder nach Abtrennen des Waschwassers wird das gereinigte Öl aus dem Reaktor entfernt. Das Öl wird nach dem Auswaschen des Aluminiums in der Regel mit Wasser gesättigt oder nahezu gesättigt sein. So kann der Anteil an Wasser im Öl beispielsweise etwa 100 ppm betragen. Zur Verringerung des Restwassers im Öl wird das Öl über eine Filtriereinrichtung geführt.After separating the aqueous metal hydroxide solution or after separating the washing water, the purified oil is removed from the reactor. The oil will usually be saturated or nearly saturated with water after the aluminum has been washed away. For example, the proportion of water in the oil can be around 100 ppm. To reduce the residual water in the oil, the oil is fed through a filter device.

Diese Filtriereinrichtung dient der Trocknung des Öls. Sie dient ferner dem Entfernen von gegebenenfalls im Öl noch vorhandenen Schwebstoffen. Die Filtriereinrichtung kann eine oder mehrere Substanzen zur chemischen oder physikalischen Bindung von Wasser enthalten. Solche Substanzen oder Trocknungsmittel umfassen beispielsweise Kieselgele, Molekularsiebe, Natriumsulfat und Magnesiumsulfat. Natriumsulfat wird besonders bevorzugt. Die Filtriereinrichtung kann als sogenannter Kerzenfilter ausgebildet sein, der mit der Substanz zur chemischen oder physikalischen Bindung von Wasser (Trocknungsmittel) befüllt ist. Durch die Trocknung des Öls werden sowohl Wasser als auch Schwebstoffe, falls solche im Öl noch vorhanden sind, aus dem Öl abgetrennt. Das erhaltene Öl ist im Wesentlichen wasserfrei. Das bedeutet, die Wassersättigung im Öl liegt zwischen 20 bis 70 % der höchstmöglichen Wassersättigung, vorzugsweise um 50 % oder weniger. Die Wassersättigung im Öl kann mit einem kapazitiven Wassersensor bestimmt oder durch Titration nach Karl Fischer bestimmt werden. Das Produktöl des erfindungsgemäßen Verfahrens ist nahezu frei von Metallabrieb. Die Ölreinheit kann durch Messung der Trübung bestimmt werden. Das so erhaltene Öl kann als Reinöl in Dressier- oder Walzverfahren wiederverwendet werden.This filter device serves to dry the oil. It also serves to remove any suspended matter still present in the oil. The filter device can contain one or more substances for chemically or physically binding water. Such substances or desiccants include, for example, silica gels, molecular sieves, sodium sulfate, and magnesium sulfate. Sodium sulfate is particularly preferred. The filter device can be designed as a so-called candle filter be filled with the substance for chemically or physically binding water (desiccant). By drying the oil, both water and suspended matter, if any are still present in the oil, are separated from the oil. The oil obtained is essentially anhydrous. This means that the water saturation in the oil is between 20 and 70% of the highest possible water saturation, preferably around 50% or less. The water saturation in the oil can be determined with a capacitive water sensor or by titration according to Karl Fischer. The product oil of the process according to the invention is almost free of metal abrasion. Oil cleanliness can be determined by measuring turbidity. The oil obtained in this way can be reused as pure oil in skin-passing or rolling processes.

Die wässrige gelöstes Aluminium enthaltende Phase kann neutralisiert werden. Die Neutralisation kann beispielsweise durch Zugabe von Schwefelsäure erfolgen. Dabei fallen Aluminiumhydroxid und gegebenenfalls weitere Metallhydroxide aus. Bei der Fällung von Aluminiumhydroxid werden Schwebstoffe und restliches Öl eingeschlossen, mitgefällt und vom Wasser getrennt. Nach Trennung von Wasser und Festphase kann das so erhaltene Wasser oftmals ohne weitere Behandlung aber in Einklang mit den Anforderungen für Direkteinleiter in die Kanalisation geleitet werden.The aqueous phase containing dissolved aluminum can be neutralized. The neutralization can take place, for example, by adding sulfuric acid. Aluminum hydroxide and, if appropriate, other metal hydroxides are precipitated in the process. During the precipitation of aluminum hydroxide, suspended matter and the remaining oil are trapped, precipitated and separated from the water. After separation of water and solid phase, the water obtained in this way can often be discharged into the sewage system without further treatment, but in accordance with the requirements for direct dischargers.

Das Auswaschen des Aluminiums aus dem Öl kann auch in zwei parallel geschalteten Reaktoren im sogenannten Pendel-Chargenbetrieb erfolgen, oder es werden unterschiedliche Verfahrensstufen des erfindungsgemäßen Verfahren parallel in beiden Reaktoren durchgeführt.The aluminum can also be washed out of the oil in two reactors connected in parallel in so-called pendulum batch operation, or different process stages of the process according to the invention can be carried out in parallel in both reactors.

Das erfindungsgemäße Verfahren kann bei Umgebungstemperatur durchgeführt werden. Es ist keine Zufuhr von Energie in Form von Wärme erforderlich. Das Verfahren kann batchweise oder kontinuierlich durchgeführt werden.The process of the invention can be carried out at ambient temperature. No supply of energy in the form of heat is required. The process can be carried out batchwise or continuously.

Nachfolgend wird eine Ausführungsform des erfindungsgemäßen Verfahrens unter Berücksichtigung von Fig. 1 beispielhaft erläutert.An embodiment of the method according to the invention, taking into account 1 explained as an example.

Das Dressieren von Aluminiumblech in einem Dressierwalzgerüst 1 erfolgt unter Zusatz eines Dressieröls als Kühlschmierstoff (8 bis 10 l/min). Dazu wird das Dressieröl aus einem Reinöltank 1 zum Dressierwalzgerüst 1 gefördert. Über die Leitung 3 wird das gebrauchte mit Aluminium angereicherte Dressieröl in den Staubehälter 4 für verunreinigtes Dressieröl überführt. Durch Leitung 5 wird das verunreinigte Öl in den Reaktor 7 geleitet. Reaktor 7 ist mit einem Propellerrührer 8 und einem Druckbelüfter 9 ausgerüstet. Durch den Druckbelüfter 9 soll die Anreicherung von Wasserstoffgas im Reaktor 7 vermieden werden. In einem Batchverfahren ist verdünnte Alkalimetallhydroxidlösung im Reaktor 7 im etwa 10fachen stöchiometrisch Überschuss, bezogen auf Aluminium als 2 bis 3%ige Natronlauge vorgelegt worden, bevor über Leitung 5 verunreinigtes Öl in den Reaktor zum Auswaschen der Aluminiumpartikel geführt wird. Über die Leitungen 5 und 6 kann auch die verdünnte Alkalimetallhydroxidlösung in den Reaktor 7 geleitet werden. Alkalimetallhydoxid kann als höher konzentrierte Lösung in einem Vorratstank 10 gelagert werden. Zur Einstellung der gewünschten Alkalimetallhydroxid-Konzentration wird flüssige Alkalimetallhydroxidlösung aus dem Vorratstank 10 über Leitung 11 in einen Mischer überführt und dort unter Zugabe von Wasser aus Quelle 14 über Leitung 13 auf die gewünschte Konzentration gebracht. Im nach unten konisch ausgebildeten Reaktor 7 erfolgt eine intensive Durchmischung des mit Aluminium verunreinigten und gebrauchten Walzöls mit der Alkalimetallhydroxidlösung mit Hilfe des Propellerührers 8. Durch das Durchmischen von Alkalimetallhydroxidlösung und Walzöl oder Dressieröl soll eine weitgehende Überführung des metallischen Aluminiums in Aluminiumhydroxid erfolgen. Anschließend führt man im Reaktor 7 eine Phasentrennung von wässriger alkalischer Phase und Ölphase herbei. Das Ausmaß der Phasentrennung wird durch Messung der elektrischen Leitfähigkeit bestimmt. Ist die Phasentrennung im Reaktor weitgehend abgeschlossen, wird die wässrige alkalische Phase am Boden des Reaktors abgelassen und über Leitung 19 zur weiteren Behandlung 20 wie der Neutralisation geführt. Anschließend wird die Ölphase aus dem Reaktor 7 abgelassen und über Leitung 15 zu einem Kerzenfilter 16 geführt. Im Kerzenfilter 16 erfolgt die Trocknung des Öls. Ferner werden Schwebstoffe beim Durchströmen des Filters 16 im Filtermaterial zurückgehalten. Das aus dem Filter abfließende Öl wird über Leitung 17 in den Reinöltank 1 geleitet. Von dort kann es wieder dem Dressierwalzgerüst 2 zur Verwendung in einem Dressierverfahren zugeführt werden.The skin-passing of aluminum sheet in a skin-pass rolling stand 1 takes place with the addition of a skin-pass oil as a cooling lubricant (8 to 10 l/min). For this purpose, the skin-pass oil is conveyed from a pure oil tank 1 to the skin-pass mill stand 1 . The used skin-passing oil enriched with aluminum is transferred via the line 3 into the accumulation tank 4 for contaminated skin-passing oil. The contaminated oil is fed into the reactor 7 through line 5 . Reactor 7 is equipped with a propeller stirrer 8 and a pressure aerator 9. The enrichment of hydrogen gas in the reactor 7 is to be avoided by the pressurized aerator 9 . In a batch process, dilute alkali metal hydroxide solution is introduced into reactor 7 in about a 10-fold stoichiometric excess, based on aluminum, as 2 to 3% sodium hydroxide solution before contaminated oil is fed into the reactor via line 5 to wash out the aluminum particles. The dilute alkali metal hydroxide solution can also be fed into the reactor 7 via the lines 5 and 6 . Alkali metal hydroxide can be stored in a storage tank 10 as a more concentrated solution. To set the desired alkali metal hydroxide concentration, liquid alkali metal hydroxide solution is transferred from storage tank 10 via line 11 into a mixer and brought to the desired concentration there by adding water from source 14 via line 13 . In the reactor 7, which is conical in design at the bottom, the used rolling oil contaminated with aluminum is intensively mixed with the alkali metal hydroxide solution using the propeller stirrer 8. By mixing the alkali metal hydroxide solution and rolling oil or skin-pass oil, the metal aluminum is to be largely converted into aluminum hydroxide. A phase separation of the aqueous alkaline phase and the oil phase is then brought about in the reactor 7 . The extent of phase separation is determined by measuring the electrical conductivity. If the phase separation in the reactor is largely complete, the aqueous alkaline phase is drained off at the bottom of the reactor and conducted via line 19 for further treatment 20 such as neutralization. The oil phase is then drained from the reactor 7 and fed to a candle filter 16 via line 15 . The oil is dried in the candle filter 16 . Furthermore, suspended matter is retained in the filter material as it flows through the filter 16 . The oil flowing out of the filter is fed to the clean oil tank 1 via line 17 directed. From there it can be fed back to skin-pass mill 2 for use in a skin-pass process.

Claims (6)

  1. Method for recycling oils contaminated with aluminum abrasion from rolling/skin pass processes, characterized in that the rolling or skin pass oil contaminated with aluminum is mixed with an aqueous alkali metal hydroxide solution, a separation between an aqueous phase and an oil phase is brought about, the aqueous phase is subsequently separated from the oil phase, and residual water and possibly present suspended substances are removed from the oil phase using a drying agent, the mass ratio of contaminated rolling or skin pass oil to aqueous alkali metal hydroxide solution being 1 to at least 2.
  2. Method according to claim 1, characterized in that a rolling or skin pass oil having a metal aluminum content of 0.01 to 5 g/L is used as the contaminated oil.
  3. Method according to either claim 1 or claim 2, characterized in that the aqueous alkali metal hydroxide solution is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
  4. Method according to any of claims 1 to 3, characterized in that the treatment of the rolling or skin pass oil contaminated with aluminum is carried out using the aqueous alkali metal hydroxide solution in the presence of a watersoluble polyalkylene glycol, alkylene being ethylene and/or propylene.
  5. Method according to any of claims 1 to 4, characterized in that the separation of the aqueous phase and the rolling oil phase is facilitated by the addition of a polyalkylene glycol which at any mixing ratio is completely soluble in water at 20°C without phase separation.
  6. Method according to any of claims 1 to 5, characterized in that the mixing of the rolling or skin pass oil contaminated with aluminum is conducted in a reactor equipped with a stirrer at room temperature, and the separation of the aqueous phase from the oil phase is carried out in such a way that the purified rolling oil phase can be discharged from the upper part of the reactor by supplying water or an aqueous liquid into the lower part of the reactor.
EP18171973.3A 2017-05-17 2018-05-14 Washing method for rolling and dressing oils Active EP3404084B1 (en)

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CN114522992B (en) * 2022-03-08 2024-01-02 金龙电缆科技有限公司 Method for recycling aluminum wiredrawing lubricating liquid

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US2902439A (en) * 1958-07-03 1959-09-01 Aluminum Co Of America Reclamation of aluminum fabricating lubricants
DE1545299A1 (en) 1965-11-15 1969-06-26 Focsaneanu Dr Ing Otto A Process for the removal of alien and intrinsic aging products from alloyed and unalloyed waste oils, such as engine and gearbox drainage, or. heavily contaminated hydrocarbon solvents
CH595435A5 (en) 1975-04-10 1978-02-15 Alusuisse
US4256578A (en) * 1979-11-29 1981-03-17 Amsted Industries Incorporated Waste oil recovery process
GB201506238D0 (en) * 2015-04-13 2015-05-27 3D Eco Oil Ltd A Lubricant

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JP2019022906A (en) 2019-02-14

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