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EP0228651B1 - Procédé d'obtention de lubrifiants de haute qualité à partir d'huiles usées - Google Patents

Procédé d'obtention de lubrifiants de haute qualité à partir d'huiles usées Download PDF

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Publication number
EP0228651B1
EP0228651B1 EP86117551A EP86117551A EP0228651B1 EP 0228651 B1 EP0228651 B1 EP 0228651B1 EP 86117551 A EP86117551 A EP 86117551A EP 86117551 A EP86117551 A EP 86117551A EP 0228651 B1 EP0228651 B1 EP 0228651B1
Authority
EP
European Patent Office
Prior art keywords
oils
oil
waste
boiling
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86117551A
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German (de)
English (en)
Other versions
EP0228651A1 (fr
Inventor
Karl-Heinz Keim
Hartmut Dr. Hammer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RWE Entsorgung AG
Original Assignee
RWE Entsorgung AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RWE Entsorgung AG filed Critical RWE Entsorgung AG
Priority to AT86117551T priority Critical patent/ATE62928T1/de
Publication of EP0228651A1 publication Critical patent/EP0228651A1/fr
Application granted granted Critical
Publication of EP0228651B1 publication Critical patent/EP0228651B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning

Definitions

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

Landscapes

  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (2)

  1. Procédé de préparation de lubrifiants de haute qualité à partir de huiles usées par l'hydrogénation catalytique des huiles usées ou des mélanges renfermant de l'huile et de l'hydrogène et/ou des gaz contenant de l'hydrogène et/ou des solvants entraînant de l'hydrogène, libérés, le cas échéant, des matières solides, d'autres additifs dissouts et/ou émulsifiés et d'eau et traités préalablement, le cas échéant, chimiquement et/ou physiquement, caractérisé en ce qu'on réalise le traitement hydrogénant en présence d'un ou de plusieurs catalyseur(s) hydrocraquant(s) à des températures de 350-480 °C, des pressions de 20-400 bars et une vitesse spatiale liquide horaire de 2-20 1/1 x h et qu'on réduit la quantité des composés ayant un point d'ébullition supérieur à 350 °C de 20-70 %.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme catalyseur hydrocraquant un catalyseur amorphe et qu'on réalise le traitement hydrogénant à une température de 400 - 460 °C, une pression de 100-350 bars et une vitesse spatiale liquide horaire de 4-12 1/1 x h et qu'on réduit la quantité des composés ayant un point d'ébullition supérieur à 350 °C.
EP86117551A 1986-01-02 1986-12-17 Procédé d'obtention de lubrifiants de haute qualité à partir d'huiles usées Expired - Lifetime EP0228651B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86117551T ATE62928T1 (de) 1986-01-02 1986-12-17 Verfahren zur gewinnung hochwertiger schmierstoffe aus altoelen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3600024 1986-01-02
DE3600024A DE3600024C1 (de) 1986-01-02 1986-01-02 Verfahren zur Gewinnung hochwertiger Schmierstoffe aus Altoelen

Publications (2)

Publication Number Publication Date
EP0228651A1 EP0228651A1 (fr) 1987-07-15
EP0228651B1 true EP0228651B1 (fr) 1991-04-24

Family

ID=6291373

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86117551A Expired - Lifetime EP0228651B1 (fr) 1986-01-02 1986-12-17 Procédé d'obtention de lubrifiants de haute qualité à partir d'huiles usées

Country Status (5)

Country Link
EP (1) EP0228651B1 (fr)
AT (1) ATE62928T1 (fr)
DE (2) DE3600024C1 (fr)
ES (1) ES2000018B3 (fr)
GR (2) GR880300005T1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3723607A1 (de) * 1987-07-17 1989-01-26 Ruhrkohle Ag Verfahren zum hydrierenden aufarbeiten von altoelen
ES2020603B3 (es) * 1987-07-23 1991-08-16 Uop (A New York General Partnership) Tratamiento de un efluente residual hidrocarbonaceo sensible a la temperatura que contiene un componente no - destilable
DE3839799A1 (de) * 1988-11-25 1990-07-05 Rwe Entsorgung Ag Verfahren zur aufarbeitung kontaminierter oele
DE102006057910A1 (de) * 2006-12-08 2008-07-03 Exad Gmbh Verfahren zum Aufbereiten von Altölen und/oder Öl/Wassergemischen oder ähnlichen flüssigen Gemischen
FI128237B (en) * 2018-12-21 2020-01-15 Neste Oyj METHOD FOR UPGRADING GAME OILS

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980551A (en) * 1975-12-18 1976-09-14 Hydrocarbon Research, Inc. Refining of waste lube oil to prepare usable lubestock

Also Published As

Publication number Publication date
DE3600024C1 (de) 1987-06-19
ATE62928T1 (de) 1991-05-15
GR880300005T1 (en) 1989-06-22
EP0228651A1 (fr) 1987-07-15
ES2000018B3 (es) 1992-01-01
DE3678922D1 (de) 1991-05-29
ES2000018A4 (es) 1987-09-01
GR3001851T3 (en) 1992-11-23

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