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
• • 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
• • 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

Definitions

• the present invention relates to a process for working up, in particular for dehalogenating, waste oil.
• Regenerative oils are subject to requirements if they are used as base oils for the renewed production of lubricating oils.
• oils are subject to or has to be restricted for technical reasons when using the regenerated oils as base oils, these include inorganic and organic compounds of metals, sulfur, phosphorus and halogens, especially chlorine.
• Chlorine compounds have a special position because
• Halogen compounds from waste oils up to residual contents of less than 100 mg chlorine / kg oil have so far been technically hardly possible with reasonable effort.
• Waste oils up to the concentration range of 100 mg / kg (expressed as chlorine) are known in various processes. They exist e.g. in an aftertreatment with chlorine-binding additives, such as alkali or
• Alkaline earth metals alkali or alkaline earth hydroxides, such as sodium or potassium hydroxide or calcium and
• halogen and the other reaction products can be in a form which is difficult to separate, e.g. B. as difficult filterable or centrifugable sludge. You can create residues, which additional
• Halogen binders can also increase the ash content of the processed oil too much. Finally, they require special security devices and
• US-PS 39 30 988 discloses a method for
• Ammonium sulfate and / or ammonium bisulfate for reaction with the metal-containing components of the oil and for the formation of metal-containing solids is brought into contact, the reaction mass in an oil phase and an aqueous phase
• Ammonium phosphate is contacted to react with the metal salts contained in the oil, the
• the resulting precipitate is allowed to settle and the oil is separated from the water and the precipitate.
• US Pat. No. 4,151,072 discloses a process for obtaining pure lubricating oil from used lubricating oil, in which the oil is mixed with an aqueous solution of an ammonium salt selected from ammonium sulfate, ammonium bisulfate,
• Ammonium phosphate diammonium hydrogen phosphate
• Ammonium dihydrogen phosphate and mixtures thereof, in sufficient amount is brought into contact at a temperature of 60 to 120 ° C, most of the water and light hydrocarbons are removed from the mixture obtained at a temperature of 110 to 140 ° C, the oil phase is separated by filtration, the filtered oil to a Temperature of 200 to 480 ° C is heated and in contact with an adsorbent
• DE-AS 25 08 713 discloses a method for
• the dehalogenation is carried out by treating the oil with an alkali metal, in particular Na or K, an alkaline earth metal,
• Mg or Ca an alkali, alkaline earth or aluminum alcoholate, an alkali hydride or
• an organic base especially pyridine or piperidine, or with metallic aluminum or
• DE-OS 36 37 255 discloses a method for
• the hydrogenated product ammonia is added and degassed, and an aqueous phase containing ammonium chloride is separated from the degassed product.
• DE-OS 36 21 175 discloses a method for
• hydrocarbon oils in which the hydrocarbon oils are treated in a homogeneous phase with alkali or alkaline earth alcoholates whose alkyl groups have 6 to 25 carbon atoms at 120 to 400 ° C. and the
• DE-PS 36 00 024 discloses a process for obtaining high-quality lubricants from waste oils by catalytically hydrogenating treatment of freed from solids, other dissolved and / or emulsified additives and water and optionally chemically and / or
• GB-PS 85 67 64 discloses a process for reducing the acidity of used lubricating oil, in which the oil is treated with ammonia.
• the object of the present invention is to provide a process for working up, in particular for dehalogenating, waste oil, in which the waste oil in a simple technical and economical manner contained foreign substances, especially halogens, can be removed.
• This object is achieved by a process of the type mentioned at the outset, which is characterized in that a) the waste oil at temperatures up to 150 ° C. with an effective amount of an aqueous solution of at least one strong acid and / or at least one salt of a weak one Treated base and a strong acid or a precursor thereof, b) treating the product obtained at elevated temperatures with at least one halogen binder and c) separating the oil from the water and / or the solids in the product thus obtained.
• the method according to the invention enables waste oil to be processed using small amounts of non-toxic or non-hazardous chemicals without applying pressure at relatively low temperatures.
• Dehalogenation also results in a sharp reduction in the phosphorus and metal content of the waste oil.
• An oil worked up by the process according to the invention is suitable as a preliminary stage for re-refining.
• Step a) of the method according to the invention is preferably carried out in a stripping device. Temperatures of up to 150 ° C, in particular from 20 to 150 ° C, particularly preferably from 80 to 120 ° C, are generally used. The treatment time is preferably 1 to 2 hours.
• the waste oil is treated with an effective amount of an aqueous solution of at least one strong acid and / or at least one salt of a weak base and a strong acid or a precursor thereof.
• the amount of solution used depends on the amount of oil used
• aqueous solution based on the waste oil.
• amounts below 5% by weight aqueous solution, based on the waste oil are sufficient. Amounts below 0.2% by weight are particularly preferably used. All strong acids can be used to treat the waste oil in stage a).
• Phosphonic acid hydrochloric acid, hydrofluoric acid or mixtures thereof are used.
• Phosphonic acid Ortho-, meta- and polyphosphoric acid can be used as phosphoric acid.
• the weak base and strong acid salt is preferably an ammonium salt of a strong acid.
• Ammonium phosphonic acid, ammonium chloride, ammonium fluoride or mixtures thereof are suitable.
• Diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite and ammonium phosphonic acid are dimonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite and ammonium phosphonic acid.
• Ammonium phosphite can be used as mono-, di- and tri-ammonium phosphite.
• step a) a salt of guanidine, an amide, such as carbamide or hydrazine, or else an alkyl or aryl compound of the above acids, such as
• Dimethyl phosphite, diethyl phosphite or triethyl phosphite can be used.
• the dissolved and undissolved organic decompose
• Halogen compounds to hydrogen halides which are immediately neutralized by the halogen binders added.
• the coagulation temperature is preferably 250 to 300 ° C and the treatment time 0.5 to 24
• Halogen binder is preferably ammonia and / or an organic base.
• organic bases are urea, guanidine, hydrazine, hydrazine hydrate
• Carbazide a semicarbazide, piperazine, phenylenediamine, morpholine, diethanolamine, triethanolamine or a salt of these compounds are particularly preferred.
• the coagulation can be carried out in such a way that the oil is heated in three stages via special ones
• Heat exchanger in that it mostly remains in the respective cycle and is led over trickle towers.
• the halogens are added by adding ammonia and / or an organic base
• the product obtained is separated from the water and / or the solids. Since it's easy
• sedimentable it can be decanted, for example, with about 95% of the water and / or
• Solids are separated. Depending on the viscosity, the oil can then be reheated somewhat, for example to a temperature of 60 to 150 ° C., and then filtered, for example pressed through a filter press. The remaining solids are removed.
• the mixture obtained in stage a) can be cured before coagulation. This can
• step e c for example by adding an additive for better separation of the oil in step e c), preferably at a temperature of 140 to 200 ° C and over 1 to 2 hours.
• additives are preferred
• Treatment times can be shortened.
• stage b) Separation.
• This post-treatment can be carried out over 1 to 24 hours. Such post-treatment is particularly suitable if one
• stage a the smallest possible amount of the aqueous solution is used in stage a), for example less than 0.2% by weight of the aqueous solution, based on the waste oil.
• any customary pretreatment can be carried out before the waste oil is treated by the process according to the invention.
• a pre-dewatering such as by centrifuging, decanting or distilling, can be carried out with a proportion of more than 5% of foreign substances.
• the oil prepared by the method according to the invention is particularly suitable for use as a heating oil or as a base oil for the renewed production of lubricating oils.
• Carbonic acid diamide and diethanolamine (4.0 g total) added. After 4 hours the mixture was cooled and filtered clear at 150 ° C. over a suction filter with 1% silica. The filtrate still contained 140 ppm chlorine, 8 ppm phosphorus and had an ash content of 0.01%.
• Example 4 In this example, the same starting oil, unfiltered waste oil with a chlorine content of 1,840 mg / kg and an ash content of 0.37% was examined in each case. The process was varied with regard to the agents added, while the further conditions, namely temperature and treatment time, were kept constant in the respective process steps a) and b).
• Step a) was carried out by treating the waste oil at 70 ° C before stripping to 140 ° C.
• Step b) was carried out at 280 ° C for five hours.
• Table 1 shows the compounds added in stages a) and b) and the chlorine and ash content determined in the filtered oil after carrying out these stages, and the filterability of the oil after coagulation over five hours at 280 ° C.
• the chlorine content of the waste oil is reduced to a certain extent, while the ash content is not reduced.
• stage b) of the process according to the invention alone does not lead to the desired dehalogenation of the waste oil. Rather, stage a) destabilizes the organochlorine compounds, which are then almost completely removed in stage b) (test 4).
• the waste oil was treated according to stage a) of the process according to the invention, while no halogen binder was added in stage b). A sufficient reduction in the ash content is achieved; however, the chlorine content is only minimally reduced.
• stage a) serves both the demetallization and the destabilization of the chlorine compounds.
• the demetallization is not yet complete after stage a), but the heat treatment in stage b) is required in order to achieve complete demetallization and also to make the waste oil filterable.
• the dehalogenation according to stage a) is only achieved to the degree as in the waste oil
• Chlorine content (mg / kg): 1870 Ash content (%): 0, 37

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Lubricants (AREA)
• Removal Of Specific Substances (AREA)
• Processing Of Solid Wastes (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Applications Claiming Priority (2)

Publications (1)

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• 1989
  • 1989-01-04 DE DE3900159A patent/DE3900159A1/de not_active Withdrawn
  • 1989-11-03 US US07/431,946 patent/US5057207A/en not_active Expired - Fee Related
  • 1989-12-14 ZA ZA899547A patent/ZA899547B/xx unknown
  • 1989-12-21 MY MYPI89001831A patent/MY104878A/en unknown
• 1990
  • 1990-01-03 WO PCT/EP1990/000004 patent/WO1990007566A1/de not_active Application Discontinuation
  • 1990-01-03 HU HU901670A patent/HUT61584A/hu unknown
  • 1990-01-03 JP JP2502320A patent/JPH04504432A/ja active Pending
  • 1990-01-03 CA CA002007062A patent/CA2007062A1/en not_active Abandoned
  • 1990-01-03 KR KR1019900701969A patent/KR910700325A/ko not_active Application Discontinuation
  • 1990-01-03 PT PT92778A patent/PT92778A/pt not_active Application Discontinuation
  • 1990-01-03 EP EP90902193A patent/EP0452409A1/de not_active Ceased
  • 1990-01-03 YU YU190A patent/YU46735B/sh unknown
  • 1990-01-03 AU AU49495/90A patent/AU4949590A/en not_active Abandoned
  • 1990-01-03 BR BR909006991A patent/BR9006991A/pt not_active Application Discontinuation
  • 1990-01-04 CN CN90100011A patent/CN1043954A/zh active Pending

Non-Patent Citations (1)

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