EP0270813A1 - Procédé de récupération d'huile usée - Google Patents

Procédé de récupération d'huile usée Download PDF

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Publication number
EP0270813A1
EP0270813A1 EP87115860A EP87115860A EP0270813A1 EP 0270813 A1 EP0270813 A1 EP 0270813A1 EP 87115860 A EP87115860 A EP 87115860A EP 87115860 A EP87115860 A EP 87115860A EP 0270813 A1 EP0270813 A1 EP 0270813A1
Authority
EP
European Patent Office
Prior art keywords
oil
gas
waste oil
rich
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.)
Ceased
Application number
EP87115860A
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German (de)
English (en)
Inventor
Johannes Dr. Albrecht
Rainer Dr. Reimert
Joachim Dr. Wilhelm
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.)
Reimert Rainer Dr-Ing
Wilhelm Joachim Dr-Ing
Original Assignee
Reimert Rainer Dr-Ing
Wilhelm Joachim Dr-Ing
Metallgesellschaft 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 Reimert Rainer Dr-Ing, Wilhelm Joachim Dr-Ing, Metallgesellschaft AG filed Critical Reimert Rainer Dr-Ing
Publication of EP0270813A1 publication Critical patent/EP0270813A1/fr
Ceased 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
    • 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
    • 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
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents

Definitions

  • the invention relates to a method for processing used oil.
  • This waste oil can e.g. are used motor oil, gear oil, lubricating oil, hydraulic oil, transformer oil or similar oils or mixtures of these oils.
  • Used oil contains various types of impurities that come from previous use, so used lubricating oil contains various additives and polychlorinated diphenyls (PCBs) that are highly toxic. If you want to recycle the used oil for reuse, you have to remove most of the contaminants and especially the halides, including PCB.
  • PCBs polychlorinated diphenyls
  • the object of the invention is to remove non-distillable impurities on the one hand and, on the other hand, halogen and heteroatom-containing components when working up waste oil.
  • the non-distillable impurities are primarily high-boiling aging products, additives and solids in waste oil, and the halogen-containing components in particular are PCBs.
  • the aim of the process is also to minimize the amount of waste to be disposed of.
  • this is achieved in that the waste oil is mixed with hydrogen-rich gas at a pressure of 50 to 250 bar, heated to a temperature of 350 to 500 ° C., solids are separated in a separation zone and removed as sludge, an evaporated, oil-rich phase withdrawing the separation zone and catalytically hydrogenating at temperatures from 300 to 400 ° C, the hydrogenated product is mixed with ammonia and degassed and separating an aqueous phase containing ammonium chloride from the degassed product.
  • the undesirable high-boiling components are separated from the waste oil by distillation in the separation zone.
  • the separation takes place under high pressure of 50 to 250 bar at temperatures of 350 to 500 ° C under hydrogenating conditions. This significantly improves the manageability of the residue.
  • the oil-rich vapor phase that forms in the separation zone is e.g. hydrogenated on a standard refinery catalyst based on cobalt-molybdenum or nickel-molybdenum. Chlorine compounds, including PCB, to HCl, oxygen compounds to H2O, nitrogen compounds to NH3 and sulfur compounds to H2S are largely converted. The hydrogenation takes place in the gas or trickle phase. The undesired components are washed out of the hydrogenated product by adding ammonia as ammonium compounds. Because ammonium chloride is formed from HCl, this neutralization reduces the corrosion problems.
  • the hydrogenation gases inevitably obtained in the hydrogenation e.g. CH4, ethane and propane can be used for underfire in the heater upstream of the separation zone.
  • a further development of the invention consists in degassing the hydrogenated product after addition of ammonia water in a first degassing stage at a pressure of 50 to 250 bar and temperatures of 20 to 60 ° C, withdrawing a hydrogen-containing gas and at least partially adding the waste oil, which oily phase to 1 to 5 bar relaxed and gives up a second degassing stage and from the second degassing stage at temperatures of 20 to 60 ° C a C1- to C4 hydrocarbons containing gas, an oil-rich product and an aqueous phase containing ammonium chloride is derived separately.
  • a sludge containing solids accumulates in the separation zone, which has to be disposed of but can also be worked up further, e.g. by filtering or centrifuging to recover valuable materials such as nickel and molybdenum.
  • a process water is formed which is contaminated with ammonium salts and water-soluble organic compounds and which is easy to clean biologically because there are no toxic chlorine compounds.
  • the waste oil to be processed comes from line (1) and is first freed of coarse solids in a mechanical filter (2).
  • the waste oil is compressed to 50 to 250 bar by a pump (3) and first reaches a heat exchanger (5) in line (4), in which the waste oil is first heated.
  • Hydrogen-rich gas from line (7) is mixed with the waste oil in line (6), whereupon the temperature of the mixture in the fired heater (10) is increased to 350 to 500 ° C.
  • the waste oil in the line (11) arrives at a separator (12) of a known type. In the bottom of the separator, the unevaporated portion of the waste oil collects in the form of a sludge, the solids, high molecular weight Contains impurities, aging products and additives. This sludge is removed from the process in line (13) and, if desired, can be sent for further processing.
  • An oil-rich vapor phase leaves the separator (12) through line (14), whereby hydrogen-rich gas is added to it from line (15). It makes sense to set the temperature of the mixture with this gas, which is passed in line (14) into the hydrogenation reactor (16).
  • the entry temperatures of the mixture into the reactor (16) are in the range from 300 to 400 ° C.
  • the hydrogenation of the mixture is preferably carried out in the gas phase or in the trickle phase over a hydrogenation catalyst which is known per se and is arranged in a fixed bed.
  • a cobalt-molybdenum or nickel-molybdenum catalyst is usually used as the hydrogenation catalyst.
  • the hydrogenated product leaves the reactor (16) in line (20), it now contains HCl, NH3, H2S, H2O and other hydrogenation products instead of the impurities in the mixture in line (14).
  • the product in the line (20) releases part of its sensible heat in the heat exchanger (5).
  • the hydrogenated product is added ammonia water from line (8), in such an amount that the HCl formed is neutralized.
  • the mixture flows through a cooler (22), which it leaves at temperatures of 20 to 60 ° C in the line (23).
  • a first separation of condensate and gas phase takes place in the separator (25) at a pressure which is only slightly below the pressure prevailing in the hydrogenation reactor (16).
  • the gas that is drawn off in line (26) mainly contains hydrogen.
  • the oil-rich condensate collecting in the separator (25) flows in the line (32) to an expansion valve (33) and is expanded there to a pressure of 1 to 5 bar.
  • gas and liquid are separated again. This creates a C1 to C4 hydrocarbons containing, combustible gas which is discharged in line (35) and also used as fuel in the heater (10) via line (31).
  • the product of the process, the oil-rich phase is drawn off from the separator (34) through line (36), and waste water is removed through line (37).
  • the wastewater contains ammonium compounds and, since it is not toxic, can be subjected to a biological treatment.
  • methanol is added to the waste oil through the dashed line (9), which is split into H2 and CO in the process. This produces the hydrogen-rich hydrogenation gas and dispenses with the supply of hydrogen through line (29).
  • the methanol is split in the heater (10) by thermal decomposition and also under the conditions prevailing in the separator (12) and in the hydrogenation reactor (16).
  • Used engine oil with a total chlorine content of 0.5% by weight is processed in a test facility on a laboratory scale.
  • 1.5 kg of the used oil are compressed to 140 bar per hour and mixed with 3.5 Nm3 / h of hydrogen-rich gas with an H2 content of 98%.
  • the mixture is heated to 445 ° C. and fed to the hot separator (12), in which a separation into a liquid phase and a gas phase takes place at a temperature of approximately 440 ° C.
  • the liquid phase obtained in the bottom of the separator on average 180 to 200 g / h, is a black, pasty, tar-like residue that contains the solids contained in the waste oil.
  • the gas phase is drawn off at the top of the hot separator (12) and cooled to 380 ° C. At this temperature, it is fed to the hydrogenation reactor (16), which contains 1.2 kg of a cobalt-molybdenum refinery catalyst as a fixed bed.
  • the commercially available catalyst consists of extrusions with a diameter of 3 mm.
  • the product flows through the catalyst bed from top to bottom, the temperature rising from 380 ° C to 384 ° C. 300 g of a 2% strength ammonia water is added to the hydrogenated product by means of a metering pump.
  • the mixture is cooled to room temperature in a cooler and expanded to normal pressure.
  • the liquid product consists of a practically chlorine-free, yellowish-clear oil phase, which is obtained on average in an amount of 1.3 kg / h.
  • an aqueous phase is formed, the amount of which corresponds approximately to the amount of ammonia water added and which is about 5% by weight.
  • % Contains ammonium chloride.
  • Example 1 The system of Example 1 is fed a mixture of used motor oil and methanol with a methanol content of 5% by weight in an amount of 1.5 kg / h.
  • the total chlorine content of the mixture is 0.5% by weight.
  • the mixture is compressed to 240 bar and mixed per hour with 800 Nl of hydrogen-containing gas that is generated in the process.
  • the gas is a mixture of H2 and CO with 33 vol.% CO.
  • the further treatment of the mixture is carried out as in Example 1.
  • As products an average of 1.2 kg of a largely chlorine-free oil and 980 Nl of gas per hour, which essentially consists of H2 and CO in a ratio of 2: 1 and a proportion of C1 - Contains up to C4 hydrocarbons of about 1 to 2 vol.%.
  • the hot separator (12) produces 200 g of a pasty residue per hour, which is flowable at temperatures of at least 250 ° C. Methanol is not detected in the products, which means that it is completely split into CO and H2 in the 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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP87115860A 1986-11-03 1987-10-29 Procédé de récupération d'huile usée Ceased EP0270813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863637255 DE3637255A1 (de) 1986-11-03 1986-11-03 Verfahren zum aufarbeiten von altoel
DE3637255 1986-11-03

Publications (1)

Publication Number Publication Date
EP0270813A1 true EP0270813A1 (fr) 1988-06-15

Family

ID=6312969

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87115860A Ceased EP0270813A1 (fr) 1986-11-03 1987-10-29 Procédé de récupération d'huile usée

Country Status (2)

Country Link
EP (1) EP0270813A1 (fr)
DE (1) DE3637255A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299149A2 (fr) * 1987-07-17 1989-01-18 Ruhrkohle Aktiengesellschaft Méthode de traitement de lubrifiants usagés par hydrogénation
EP0306164A1 (fr) * 1987-08-13 1989-03-08 Uop Hydrogénation d'un courant d'hydrocarbures usés sensibles à la température
CN115820333A (zh) * 2021-09-17 2023-03-21 山东大学 一种废润滑油泥的资源化回收利用方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB856764A (en) * 1958-07-08 1960-12-21 British Petroleum Co Treatment of used diesel engine lubricating oil
EP0077564A2 (fr) * 1981-10-19 1983-04-27 Phillips Petroleum Company Enlèvement de cendres d'huiles lubrifiantes
US4387018A (en) * 1982-03-17 1983-06-07 The United States Of America As Represented By The United States Department Of Energy Method of removing polychlorinated biphenyl from oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB856764A (en) * 1958-07-08 1960-12-21 British Petroleum Co Treatment of used diesel engine lubricating oil
EP0077564A2 (fr) * 1981-10-19 1983-04-27 Phillips Petroleum Company Enlèvement de cendres d'huiles lubrifiantes
US4387018A (en) * 1982-03-17 1983-06-07 The United States Of America As Represented By The United States Department Of Energy Method of removing polychlorinated biphenyl from oil

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299149A2 (fr) * 1987-07-17 1989-01-18 Ruhrkohle Aktiengesellschaft Méthode de traitement de lubrifiants usagés par hydrogénation
EP0299149A3 (fr) * 1987-07-17 1989-03-08 Ruhrkohle Aktiengesellschaft Méthode de traitement de lubrifiants usagés par hydrogénation
EP0306164A1 (fr) * 1987-08-13 1989-03-08 Uop Hydrogénation d'un courant d'hydrocarbures usés sensibles à la température
AU613714B2 (en) * 1987-08-13 1991-08-08 Uop Treating a temperature-sensitive hydrocarbonaceous waste stream to produce a hydrogenated distillable and reusable hydrocarbonaceous product stream
CN115820333A (zh) * 2021-09-17 2023-03-21 山东大学 一种废润滑油泥的资源化回收利用方法
CN115820333B (zh) * 2021-09-17 2024-01-26 山东大学 一种废润滑油泥的资源化回收利用方法

Also Published As

Publication number Publication date
DE3637255A1 (de) 1988-05-05

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