EP0299149A2 - Méthode de traitement de lubrifiants usagés par hydrogénation - Google Patents

Méthode de traitement de lubrifiants usagés par hydrogénation Download PDF

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Publication number
EP0299149A2
EP0299149A2 EP88105856A EP88105856A EP0299149A2 EP 0299149 A2 EP0299149 A2 EP 0299149A2 EP 88105856 A EP88105856 A EP 88105856A EP 88105856 A EP88105856 A EP 88105856A EP 0299149 A2 EP0299149 A2 EP 0299149A2
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EP
European Patent Office
Prior art keywords
hydrogenation
oils
products
waste
oil
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.)
Withdrawn
Application number
EP88105856A
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German (de)
English (en)
Other versions
EP0299149A3 (fr
Inventor
Josef Dr. Langhoff
Alfons Dr. Jankowski
Harald Dr. Weber
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.)
RAG AG
Original Assignee
Ruhrkohle 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 Ruhrkohle AG filed Critical Ruhrkohle AG
Publication of EP0299149A2 publication Critical patent/EP0299149A2/fr
Publication of EP0299149A3 publication Critical patent/EP0299149A3/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/908—Organic
    • Y10S210/909—Aromatic compound, e.g. pcb, phenol

Definitions

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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)
EP88105856A 1987-07-17 1988-06-23 Méthode de traitement de lubrifiants usagés par hydrogénation Withdrawn EP0299149A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873723607 DE3723607A1 (de) 1987-07-17 1987-07-17 Verfahren zum hydrierenden aufarbeiten von altoelen
DE3723607 1987-07-17

Publications (2)

Publication Number Publication Date
EP0299149A2 true EP0299149A2 (fr) 1989-01-18
EP0299149A3 EP0299149A3 (fr) 1989-03-08

Family

ID=6331743

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88105856A Withdrawn EP0299149A3 (fr) 1987-07-17 1988-06-23 Méthode de traitement de lubrifiants usagés par hydrogénation

Country Status (9)

Country Link
US (1) US5045179A (fr)
EP (1) EP0299149A3 (fr)
JP (1) JPS6436694A (fr)
AU (1) AU620335B2 (fr)
BR (1) BR8803532A (fr)
CA (1) CA1314257C (fr)
DE (1) DE3723607A1 (fr)
PL (1) PL152064B1 (fr)
ZA (1) ZA883815B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545509A1 (fr) * 1991-11-21 1993-06-09 VAW Aluminium AG Catalyseur, sa utilisation et procédé pour l'hydrodéhalogénation de composés organiques halogénés
FR2687684A1 (fr) * 1992-02-24 1993-08-27 Font Pierre Amelioration des traitements des huiles usagees et autres.
US5490919A (en) * 1990-08-14 1996-02-13 State Of Isreal, Atomic Energy Commission Process for the dehalogenation of organic compounds
EP0887087A3 (fr) * 1997-06-26 1999-01-20 ENEL S.p.A. Procédé d'élimination de polychlorobiphényles d'huiles minérales

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3840565A1 (de) * 1988-08-15 1990-02-22 Ruhrkohle Ag Verfahren zur hydrierung von organochlorverbindungen und neutralisation des anfallenden chlorwasserstoffs sowie neutralisationsmittel fuer aus organochlorverbindungen anfallenden chlorwasserstoff
US6805062B2 (en) * 1988-09-20 2004-10-19 Edward Carlton Shurtleff Apparatus and method for reclaiming useful oil products from waste oil including hydrogen injection
EP0371201A1 (fr) * 1988-12-01 1990-06-06 Ruhrkohle Aktiengesellschaft Procédé d'hydrogénation des composés organochlorés et de neutralisation du gaz chlorhydrique en résultant ainsi qu'un agent de neutralisation pour le gaz chlorhydrique résultant des composés organochlorés
GB9207236D0 (en) * 1992-04-02 1992-05-13 Grosvenor Power Services Ltd Treatment of liquids
US5753126A (en) * 1995-06-29 1998-05-19 Sandia Corporation System for increasing corona inception voltage of insulating oils
DE19852007C2 (de) 1998-11-11 2002-06-13 Mineraloel Raffinerie Dollberg Verfahren zur Wiederaufarbeitung von Altölen
US8366912B1 (en) 2005-03-08 2013-02-05 Ari Technologies, Llc Method for producing base lubricating oil from waste oil
KR100807700B1 (ko) 2007-12-27 2008-03-03 주식회사 쌍용화학 폴리염화비페닐 함유 폐유 및 이를 내장한 폐기기 재활용장치 및 방법
DE102009030061A1 (de) * 2009-06-22 2010-12-30 Chemische Werke Kluthe Gmbh Synthetisches Öl, dessen Verwendung sowie eine Additivkombination
TWI414592B (zh) 2010-11-05 2013-11-11 Ind Tech Res Inst 油品改質的方法
JP6199973B2 (ja) 2012-08-24 2017-09-20 サウジ アラビアン オイル カンパニー 溶存水素を含有する原料のためのハイドロビスブレーキング方法
US20140257008A1 (en) 2013-03-07 2014-09-11 Verolube, Inc. Method and apparatus for recovering synthetic oils from composite oil streams
US20150065762A1 (en) * 2013-09-04 2015-03-05 Utah State University Catalytic pyrolysis of olive mill waste
TR201816563T4 (tr) * 2014-03-17 2018-11-21 Hydrodec Dev Corporation Pty Ltd Kullanilmiş yağlarin rafi̇nasyonu.
US11534746B2 (en) 2018-04-06 2022-12-27 Utah State University Red mud compositions and methods related thereto
CN108970234B (zh) * 2018-08-21 2021-02-26 河北科技师范学院 一种光伏层压机真空泵油过滤系统

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1182377B (de) * 1962-01-09 1964-11-26 Hans Joachim Kettlitz Mineralo Verfahren zur Regenerierung von Altoelen
AT268492B (de) * 1964-11-30 1969-02-10 Nagynyomasu Kiserleti Intezet Verfahren Regeneration von Altölen
DE2030609A1 (de) * 1969-09-09 1971-03-18 Petrolchemisches Kombinat Verfahren zur Aufarbeitung von ge brauchten Schmierölen
US4017425A (en) * 1972-11-10 1977-04-12 Shiao Shing Jen Method of activation of red mud
FR2266932B1 (fr) * 1973-03-02 1977-09-02 Thomson Brandt
US4151072A (en) * 1977-05-16 1979-04-24 Phillips Petroleum Company Reclaiming used lubricating oils
AU536822B2 (en) * 1978-11-13 1984-05-24 Waste Lubricating Oils Ltd. Refiring waste oil
US4287049A (en) * 1980-02-05 1981-09-01 Phillips Petroleum Co. Reclaiming used lubricating oils with ammonium salts and polyhydroxy compounds
DE3215727A1 (de) * 1982-04-28 1983-11-03 Rheinische Braunkohlenwerke AG, 5000 Köln Verfahren zum behandeln von rotschlamm
US4431524A (en) * 1983-01-26 1984-02-14 Norman George R Process for treating used industrial oil
US4512878A (en) * 1983-02-16 1985-04-23 Exxon Research And Engineering Co. Used oil re-refining
US4522729A (en) * 1984-07-30 1985-06-11 Phillips Petroleum Company Filtration of oil
US4559130A (en) * 1984-08-27 1985-12-17 Chevron Research Company Metals-impregnated red mud as a first-stage catalyst in a two-stage, close-coupled thermal catalytic hydroconversion process
US4559129A (en) * 1984-08-27 1985-12-17 Chevron Research Company Red mud as a first-stage catalyst in a two-stage, close-coupled thermal catalytic hydroconversion process
US4623448A (en) * 1985-03-12 1986-11-18 Moreco Energy, Inc. Removing halogenated polyphenyl materials from used oil products
DE3600024C1 (de) * 1986-01-02 1987-06-19 Union Rheinische Braunkohlen Verfahren zur Gewinnung hochwertiger Schmierstoffe aus Altoelen
DE3623430A1 (de) * 1986-07-11 1988-01-28 Veba Oel Entwicklungs Gmbh Verfahren zur hydrierenden behandlung von mit chlorbiphenylen u. dgl. kontaminierten mineraloelen
DE3637255A1 (de) * 1986-11-03 1988-05-05 Metallgesellschaft Ag Verfahren zum aufarbeiten von altoel
JPH01136650A (ja) * 1987-11-25 1989-05-29 Olympus Optical Co Ltd 接触型レーザーメス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5490919A (en) * 1990-08-14 1996-02-13 State Of Isreal, Atomic Energy Commission Process for the dehalogenation of organic compounds
EP0545509A1 (fr) * 1991-11-21 1993-06-09 VAW Aluminium AG Catalyseur, sa utilisation et procédé pour l'hydrodéhalogénation de composés organiques halogénés
FR2687684A1 (fr) * 1992-02-24 1993-08-27 Font Pierre Amelioration des traitements des huiles usagees et autres.
EP0887087A3 (fr) * 1997-06-26 1999-01-20 ENEL S.p.A. Procédé d'élimination de polychlorobiphényles d'huiles minérales

Also Published As

Publication number Publication date
AU1909388A (en) 1989-01-19
AU620335B2 (en) 1992-02-20
PL273671A1 (en) 1989-03-20
ZA883815B (en) 1989-03-29
BR8803532A (pt) 1989-02-08
JPS6436694A (en) 1989-02-07
US5045179A (en) 1991-09-03
DE3723607A1 (de) 1989-01-26
PL152064B1 (en) 1990-11-30
EP0299149A3 (fr) 1989-03-08
CA1314257C (fr) 1993-03-09

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