EP0377606A1 - Process for purifying and regenerating used oils. - Google Patents
Process for purifying and regenerating used oils.Info
- Publication number
- EP0377606A1 EP0377606A1 EP88907226A EP88907226A EP0377606A1 EP 0377606 A1 EP0377606 A1 EP 0377606A1 EP 88907226 A EP88907226 A EP 88907226A EP 88907226 A EP88907226 A EP 88907226A EP 0377606 A1 EP0377606 A1 EP 0377606A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- oil
- temperature
- oil phase
- solution
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 102
- 230000008569 process Effects 0.000 title claims description 58
- 239000010913 used oil Substances 0.000 title abstract description 6
- 230000001172 regenerating effect Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 92
- 239000002699 waste material Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002199 base oil Substances 0.000 claims description 7
- 238000004061 bleaching Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001911 terphenyls Chemical class 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- METKIMKYRPQLGS-UHFFFAOYSA-N atenolol Chemical compound CC(C)NCC(O)COC1=CC=C(CC(N)=O)C=C1 METKIMKYRPQLGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000004533 oil dispersion Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 238000004821 distillation Methods 0.000 abstract description 10
- 239000010687 lubricating oil Substances 0.000 abstract description 10
- 238000009835 boiling Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000005194 fractionation Methods 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000003463 adsorbent Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 210000002741 palatine tonsil Anatomy 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 241000270730 Alligator mississippiensis Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- -1 PCB chlorine compounds Chemical class 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- the invention relates to a process for cleaning and regenerating used oils, in particular used lubricating oils, by filtration, heat treatment and stripping of the low boilers consisting of solvent and water.
- Waste oils are used mineral oils, especially used engine and lubricating oils.
- the utility value of mineral lubricating oils is greatly affected by oxidation products, pollution ⁇ f - and other additives that accumulate during use. Products of this type no longer fully fulfill their task and must be replaced. They are referred to as waste oils and are collected for reasons of environmental protection, raw material conservation and also from an economic point of view
- Old oils mainly consist of a base oil based on mineral oil or synthetic oil, but contain considerable amounts of foreign matter, e.g. B. water, solvents, fuels, asphalt-like substances, acids, resins, ashes and additives such as antioxidants, anti-corrosion agents,
- the additives can contain halogen, sulfur and nitrogen compounds and numerous other, sometimes toxic, components.
- Waste oils are first cleaned mechanically by removing undissolved impurities and foreign substances by sedimentation, filtration or centrifugation.
- Waste oil is subjected to a refining hydrogenation over nickel-molybdenum catalysts after pretreatment with an aqueous diammonium phosphate solution.
- polychlorinated biphenyls are also said to be at least partially degraded in this process, chlorinated solvents and cleaning liquids, metalworking oils and other processing oils and their composition are intended for the regeneration of this process is not clearly identified, and insulating and transformer oils have not been obtained in the feed material. Suitable used products for this process are therefore essentially used engine oils.
- the waste oil is freed of water and dirt by sedimentation and residual water and low boilers by atmospheric distillation.
- the gas oil fraction is then separated off in a separate stage.
- the lubricating oil components are fractionated, condensed and dirt, additives and part of the oxidation products removed as a sump.
- the distillates are hydrofinished and stripped. Since acid refining is also absent in this process, additives or foreign components must either be separable by distillation or convertible by hydrogenation. Ingredients must not impair the activity of the hydrogenation catalyst, so that, for. B. Cutting oils with contents of halogenated hydrocarbons cannot be processed by this method either, see Ullmanns Encyklopadie der technical chemistry, 4th edition volume 20, page 500.
- the oxidation products and additives are likewise not removed with sulfuric acid, but rather by treatment with finely dispersed sodium, as a result of which they either polymerize or are converted into sodium salts which have such a high boiling point that the oil distils become can.
- the distillation takes place in two steps, the second of which is designed as a short-path thin-film evaporation for separating the reaction products.
- the invention has for its object to develop a universally applicable method that allows pollutants and other undesirable components from used lubricating oils and other waste oils with higher product yields and higher product quality with less process effort and in particular less landfill than according to the prior art the technology possible to remove.
- the process should in particular be suitable for special treatments, the hydrogenation or, for example, the treatment with sodium, and to bring about procedural simplifications and the associated cost reductions, for example by avoiding the catalyst poisoning when the hydrogenation stage is switched on.
- This object is achieved according to the invention by either collecting waste oils after coarse filtration
- process step (3) from the oil phase at a temperature of 100 to 140 ° C and a pressure of 20 to 100 Torr separates the low boilers consisting of water and solvent.
- dewatering takes place in particular.
- the feedstocks bind the water as a residue, which is then removed in a known manner by separation. 50 to 80% of the free water present in the waste oil is separated in this way.
- the residual water and the low boilers are then removed by distillation in process stage (3).
- the waste oil treatment according to process steps (1) to (3) is carried out in a temperature range from 50 to 140 ° C., temperatures as low as possible in this range are preferred.
- stage (3) PCB accumulation in the low boilers and water is excluded because the boiling point range of polychlorinated bi- and terphenyls is above the stripping temperature. PCB is therefore not removed in process stage (3), which ensures that the low boilers and water obtained by this process are not contaminated with PCB. This is of great importance for an environmentally friendly process for waste oil processing.
- Process stage 3 can also be carried out before process stage 2 by first separating the low boilers from the mixture obtained, then letting them settle in a decanter and finally separating the sedimented material.
- the alkali 'wass rglaslosonne and / or the Polyalkylenglykolaten preheated in particular to 30 to 60 ° C, preferably to about 50 ° C.
- the oil phase pretreated according to process steps (1) to (3) is treated further by:
- a further embodiment of the process according to the invention in particular for the treatment of waste oils containing polychlorinated bi- and terphenyls, consists in further treating the oil phase pretreated by process steps (1) to (3) by (6) pretreating the waste oil phase a temperature of 70 to 120 ° C. is heated in a closed agitator and 3 to 8 parts by weight of n-alkanes with 6 to 10 carbon atoms are added to 1 part by weight of the pretreated waste oil phase, with intensive stirring, based on the pretreated waste oil phase, 0 , 1 to 0.5% by weight of an aqueous alkali water glass solution with a pH of -9 and 0.1 to 0.5% by weight of polyalkylene glycol of the general formula
- the oil phase is treated at a temperature of ' 3E-60 ° C in an adsorber, preferably a percolate adsorber, with a filter insert, the filter insert bleaching earth or compacted
- the low boilers (n-alkanes) are separated off from the oil filtrate at a temperature of 50 to 80 ° C. and a pressure of 20 to 100 torr.
- a hydrogenation treatment step known per se can be switched between process step (3) and process step (4), in which, in the presence of a hydrogenation-active catalyst, in particular at 200 to 400 ° C. and 10 to 200 bar and preferably at 300 up to 380 ° C and 40 to 60 bar the pretreated oil phase is hydrogenated.
- a hydrogenation-active catalyst in particular at 200 to 400 ° C. and 10 to 200 bar and preferably at 300 up to 380 ° C and 40 to 60 bar the pretreated oil phase is hydrogenated.
- the filter insert of process stage (4) or (8) is regenerated if necessary by washing it free of the adsorbed material with a solvent.
- a ketone solvent is preferably used for this purpose, which in particular consists of one or more solvents each having a boiling point of 50 to 80 ° C. and is in particular acetone or methyl ethyl ketone.
- the treated oil phase is finally subjected to vacuum distillation at a temperature of 200 to 300 ° C. and a pressure of 1 to 50 torr.
- a further embodiment of the process according to the invention provides for treatment of the dry oil phase (with water content - ⁇ 0.1% by weight) after process step (3) in a manner known per se .%) with finely dispersed sodium.
- Process stages (1) to (3) are able to deliver a constant water-free oil flow, which is the most important requirement for the use of sodium. Since the oxidation products and the non-PCB chlorine compounds are largely removed by the pretreatment in this water-free oil stream, the sodium process is economically viable.
- the sodium required for the waste oil treatment is added to the pretreated waste oil in the form of a dispersion, in particular consisting of sodium particles of 5 to 10 ⁇ m in a base oil of a similar composition to motor oils.
- a dispersion in particular consisting of sodium particles of 5 to 10 ⁇ m in a base oil of a similar composition to motor oils.
- a dispersion of 33% by weight sodium is particularly suitable for the treatment of the pretreated dry oil stream.
- the amount of dispersion added is matched to the content of inorganic chlorine.
- the treatment temperature and time depend on the quality of the dry oil. Normally, one can be in a temperature range from 20 ° C to 250 ° C and in particular in a temperature range from 100 to 200 ° C and in a period of 1 to 30 minutes reliable PCB separation can be achieved.
- the method according to the invention is a mild and environmentally friendly method. At the same time, an inexpensive and simple process and apparatus technology is guaranteed. Several physical and chemical processes run in parallel in the individual process steps of the pretreatment. Both the removal of all pollutants and the preparation run under mild process conditions. Here the - 0 "filtering adsorption" is of particular importance for the cleaning of the material to be regenerated.
- the method steps of the method according to the invention are:
- the base oil obtained is characterized by a cheaper and higher viscosity index than fresh oil. All ash-forming additives - otherwise causing sludge formation - are removed. H. the ash content is practically 0% by weight. The viscosity improvement additives are largely retained, namely at least 1/3 of the corresponding additives of the fresh additive package.
- Contaminants in used oil form stable dispersions due to the presence of detergents. Additives prevent the physical separation of the contaminants by gravity and / or centrifugal force.
- the flocculants and adsorbents namely alkali water glass and polyalkylene glycol of the formula given, destabilize the dispersion. The differences in density between the oil and foreign matter phases thus take effect.
- the chlorine compounds are chemically converted and NaCl and non-chlorinated compounds are formed.
- the oxidation products are neutralized and 5 the converted and neutralized products are adsorbed.
- process stage (2) impurities and the flocculants and adsorbents are separated off.
- the flocculated, dispersed impurities are eliminated by decanters or separators as a result of the destabilization which took place in stage (1) and the density differences which became effective in stage (1) by the action of gravity or minimal centrifugal forces.
- process stage (3) the low boilers, namely polar and non-polar solvents, and water are removed.
- the solvent and adsorbent additive in process stage (6) serves for the further precipitation of finely dispersed impurities, in which case these additives bring about the removal of polychlorinated bi- and terphenylene and the solvent additive supports the subsequent stage of the filtering adsorption. If no polychlorinated bi- and terphenyls are present, the addition of the n-alkanes can be used to go directly to the filtering adsorption stage without the further addition of adsorbents - see process stage (4).
- Process stage (6) with the addition of solvent and adsorbent is followed by process stage (7), which largely corresponds to process stage (2).
- the filtering adsorption takes place in process stage (8) or (4). In this stage, the remaining dissolved and undissolved impurities and undesired residual additives are specifically bound to the adsorbents.
- the lubricating oil components (hydrocarbons) pass through the adsorbents.
- This filtering adsorption is a multi-parameter separation method, which is characterized in that two chemically different substances or two chemically different groups of substances are separated from one another due to their different adsorption capacity, by allowing a specific solvent and an adsorbent to act on the mixture.
- the filtering adsorption differs in that there is only a single phase during the separation, while the filtration requires two phases, generally solid / liquid.
- Adsorbed material namely 5 to 10% by weight of finely dispersed, dissolved oxidation products and residual additives, are desorbed with suitable solvents, solvents with a boiling point of up to 80 ° C., in particular acetone or methyl ethyl ketone.
- the adsorbent is dried at about 60 to about 120 ° C., preferably about 100 ° C., under a protective gas, preferably nitrogen, and then brought to the temperature required for process step (8).
- the adsorbent is now ready for use again and can be used continuously at these values.
- the lubricating oil components (about 1.5% by weight) contained in the adsorbent are removed by solvent rinsing, in particular with n-heptane, before regeneration of the adsorbent (with acetone or methyl ethyl ketone) and process step (6) or ( 9) fed. This step serves to increase the yield of the regrind.
- the residual additives and oxidation products obtained after evaporation of the solvent can be found as additives e.g. for asphalt processing use.
- PCBs, chlorinated dioxins, furans and aliphates with chlorine levels ⁇ 5% can be degraded in this way to below the detection limit.
- the recovered solvent is used again for solvent rinsing.
- the solvent is separated from the regenerate and returned in step (4) or (6).
- the oil phase finally obtained is a mixture of lubricating oil fractions with different flash points and viscosities, the fractions have to be separated under vacuum and temperatures above 200 ° C.
- the swamp is base oil.
- the process comprising process steps (1) to (3) can be used for decentralized waste oil processing, in that the collected waste oils are brought together in area collection points and treated in decentralized small plants according to the process comprising process steps (1) to (3) as a partial process .
- the thus treated waste oil may then in a central large-scale plant the method according to one or more of the dependent claims in particular for removing chlorine compounds and per- J- Q chlorinated bi- and terphenyls are subjected.
- Solutions effective in the concentration range 2.5 to 20% by weight.
- COMPALOX compacted aluminum oxide grain size 1.5 to 5 mm specific surface 180 to 200 m 2 / g chemical composition:
- Adsorbent regeneration with acetone, methyl ethyl ketone (technical).
- Filters used stainless steel, sieve mesh 20 ⁇ m to 200 ⁇ m; Glass fiber filter and non-woven filter. I
- Waste oil not containing PCBs was treated with n-heptane in the ratio of oil phase to n-heptane of 1: 4 parts by weight in a closed stirrer, as specified in Example 1, in the dry oil phase, and the mixture was stirred vigorously at 40 ° C. for 30 minutes .
- the oil solution was then in a decanter at 10 to 20 ° C with a throughput of 12,000 ml / h
- PCB-containing used oil was in a closed agitator, _., _. after the addition of n-heptane in the ratio of oil phase to n-heptane of 1: 4 parts by weight to the oil phase pretreated according to Example 1, with intensive stirring at 80 ° C. with a mixture of 0.25% by weight preheated to 50 ° C. Soda water glass 50/51 (alkaline) and 0.1% by weight of polyethylene glycol (average molecular weight 600, OH number 170 mgKOH / g), each based on the dry oil phase. The mixture was stirred intensively at 70 ° C. for about 110 minutes.
- the oil solution from Examples 2 and 3 was subjected to a "filtering adsorption".
- the adsorbers consisted of a stainless steel mesh (20 - 40 micron) and an adsorber j - benspackung with bleaching earth Tonsil CCG 30/60.
- the undesired oil components were adsorbed at 40 ° C. It was regenerated with n-heptane.
- the throughput of regenerated solution was 3,000 ml / h.
- the solvent n-heptane was recovered from the regenerate solution by distillation at 70 ° C. and a pressure of 50 torr.
- the regenerate obtained was a mixture of lubricating oil fractions with different flash points and viscosities.
- the fractions were separated under vacuum at 5 250-300 ° C and a pressure of 1 to 10 Torr.
- the bottom was obtained as the bottom.
- the adsorber has been regenerated by desorbing the adsorbed impurities (oxidation products, unwanted residual additives, degradation products, etc.) at 50 ° C with acetone (boiling point 56 ° C).
- the adsorber was dried under nitrogen flow at 60 ° C and made reusable.
- the acetone solution obtained was subjected to distillation in order to free the waste from the acetone.
- the acetone was used again.
- the wastes from Examples 1, 2, 3 and 4 were used as additives in the concentration range 0.5 to 5% by weight (based on bitumen) for asphalt modification.
- process stage (4) instead of process stage (4) or (8), thin-film evaporation known per se can be carried out. Likewise, following the treatment with dispersed sodium, the oil phase obtained can be subjected to thin-film evaporation instead of process step (4).
- the process according to the invention is distinguished from the processes of the prior art by numerous advantages: high economic efficiency, high operational reliability, mild treatment process, enabling decentralized disposal, partial integration into existing systems and processes, residues of the process, either completely reusable as additives or valuable materials for other products or traceable to previous process stages.
- the base oil obtained was characterized by a cheaper and higher viscosity index than the fresh oil. All ash-forming additives - otherwise causing sludge formation (in particular in the engine) - are removed, ie the base oil obtained has an ash content of almost 0.0% by weight. Finally, the additives to improve the viscosity are largely retained, in accordance with previous ones 1
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
On mélange des huiles usées, notamment des huiles lubrifiantes usées, après leur filtrage grossier, à une solution aqueuse de verre soluble et à une solution aqueuse de polyalkylène-glycol, en les agitant a une température élevée. On laisse ensuite le mélange ainsi obtenu se déposer, on en sépare le matériau sédimenté et on sépare l'eau et la fraction de bas point d'ébullition de la phase huileuse par distillation. On peut soumettre la phase huileuse sèche ainsi obtenue à une adsorption de filtrage, directement ou après un traitement en soi connu avec une dispersion de sodium, puis à un fractionnement par distillation.Used oils, especially used lubricating oils, after their coarse filtering, are mixed with an aqueous solution of water glass and an aqueous solution of polyalkylene glycol, with stirring at an elevated temperature. The mixture thus obtained is then allowed to settle, the sedimented material is separated therefrom and the water and the low boiling point fraction from the oily phase are separated by distillation. The dry oily phase thus obtained can be subjected to filter adsorption, directly or after treatment known per se with a sodium dispersion, then to fractionation by distillation.
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88907226T ATE82769T1 (en) | 1987-08-19 | 1988-08-18 | PROCESSES FOR CLEANING AND REGENERATION OF WASTE OILS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3727560 | 1987-08-19 | ||
DE3727560 | 1987-08-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0377606A1 true EP0377606A1 (en) | 1990-07-18 |
EP0377606B1 EP0377606B1 (en) | 1992-11-25 |
Family
ID=6334005
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88907226A Expired - Lifetime EP0377606B1 (en) | 1987-08-19 | 1988-08-18 | Process for purifying and regenerating used oils |
Country Status (8)
Country | Link |
---|---|
US (1) | US5141628A (en) |
EP (1) | EP0377606B1 (en) |
JP (1) | JPH02504523A (en) |
CN (1) | CN1021233C (en) |
AU (1) | AU2269788A (en) |
DE (2) | DE3890632D2 (en) |
RU (1) | RU1834902C (en) |
WO (1) | WO1989001508A1 (en) |
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US5019175A (en) * | 1989-05-11 | 1991-05-28 | The United States Of America As Represented By The Administrator, Environmental Protection Agency | Method for the destruction of halogenated organic compounds in a contaminated medium |
US5639383A (en) * | 1993-04-28 | 1997-06-17 | Ralfer, S.L. | Used mineral motor oil ecological recycling procedure |
SE512750C2 (en) * | 1993-11-29 | 2000-05-08 | Alfa Laval Separation Ab | Method of gravimetric separation of oil contaminated with particles and or water |
US6013174A (en) * | 1996-02-21 | 2000-01-11 | U.S. Filter Recovery Services (Mid-Atlantic, Inc.) | Process to remove ash-forming contaminants from used oil |
KR0171501B1 (en) * | 1996-08-28 | 1999-03-20 | 이성래 | Apparatus and process for reclaiming waste oil |
US6090273A (en) * | 1997-12-03 | 2000-07-18 | U.S. Filter Recovery Services (Mid-Altantic, Inc.) | Process to remove ash-forming contaminants from wet used oil |
US6074469A (en) * | 1998-05-01 | 2000-06-13 | Petro Source Refining Partners | Asphalt composition and method |
AU3121000A (en) * | 1998-12-18 | 2000-07-12 | Ron Waters | Process for the production of improved diesel fuels using reclaimed hydraulic oil |
US6395166B1 (en) * | 2000-08-30 | 2002-05-28 | Frederick J. Haydock | Method of reclaiming used motor oil for further use |
SE0401291D0 (en) * | 2004-05-17 | 2004-05-17 | Systemseparation Sweden Ab | Process for the purification of spent process oil |
CN101113385B (en) * | 2007-08-31 | 2010-04-14 | 冯文富 | Lubricating oil distillation separation regenerating process and equipment |
CN101927101B (en) * | 2009-06-24 | 2012-08-29 | 刘廷 | Environment-friendly waste oil recoverer |
US8492601B1 (en) * | 2012-04-12 | 2013-07-23 | OTG Research, LLC | Methods for converting used oil into fuel |
CN102746884B (en) * | 2012-07-17 | 2014-06-11 | 广东邦普循环科技有限公司 | Method and device for recycling oil products of scrapped car |
CN103961932B (en) * | 2014-04-24 | 2016-04-20 | 青海聚能钛业有限公司 | A kind of pollution treatment method of titanium ingot founding vacuum system and device |
CN104005812B (en) * | 2014-05-21 | 2016-06-29 | 连云港中再钢铁炉料有限公司 | A kind of method of machine oil filter core recycling |
RU2556221C1 (en) * | 2014-06-26 | 2015-07-10 | Государственное научное учреждение Всероссийский научно-исследовательский институт использования техники и нефтепродуктов Российской академии сельскохозяйственных наук (ГНУ ВНИИТиН Россельхозакадемии) | Method of regenerating waste synthetic motor oils |
CN104450147A (en) * | 2014-11-05 | 2015-03-25 | 华文蔚 | Environment-friendly purification method for waste oil of automobile industry |
RU2600726C2 (en) * | 2014-12-15 | 2016-10-27 | Федеральное государственное казенное военное образовательное учреждение высшего профессионального образования "Военная академия материально-технического обеспечения имени генерала армии А.В. Хрулёва" Министерства обороны Российской Федерации | Method of regenerating spent oil |
RU2592085C1 (en) * | 2015-02-03 | 2016-07-20 | Алексей Сергеевич Курочкин | Complex of deep drying and cleaning of dielectric fluids |
RU2594412C1 (en) * | 2015-04-29 | 2016-08-20 | Алексей Сергеевич Курочкин | System for deep drying, cleaning and recovery of liquid dielectrics |
RU2604736C1 (en) * | 2015-07-22 | 2016-12-10 | Алексей Сергеевич Курочкин | System for ultra-deep cleaning of dielectric fluids |
RU2614244C1 (en) * | 2016-05-30 | 2017-03-24 | Федеральное государственное бюджетное научное учреждение "Всероссийский научно-исследовательский институт использования техники и нефтепродуктов в сельском хозяйстве" (ФГБНУ ВНИИТиН) | Method for waste mineral motor oils purification |
RU2735224C1 (en) * | 2016-10-13 | 2020-10-28 | Публичное акционерное общество "Вторая генерирующая компания оптового рынка электроэнергии" | Method for regenerating fire-resistant synthetic turbine oils based on complex phosphoric acid ethers |
RU2717856C2 (en) * | 2016-11-15 | 2020-03-26 | Алексей Сергеевич Курочкин | Complex of filters for cleaning of dielectric liquids |
US10584271B2 (en) * | 2016-12-20 | 2020-03-10 | ORG Chem Group | Heat transfer fluid and process for preparing same |
CN108102681A (en) * | 2017-12-06 | 2018-06-01 | 菏泽万清源环保科技有限公司 | Hazardous waste resource regeneration method |
JP2020138922A (en) * | 2019-02-27 | 2020-09-03 | 株式会社神鋼環境ソリューション | Method of preparing dehydration solvent |
CN116622435A (en) * | 2023-05-26 | 2023-08-22 | 国网江苏省电力有限公司双创中心 | Aging power oil regeneration method based on transfer hydrogenation-resin adsorption and elution coupling technology |
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US4021333A (en) * | 1975-08-27 | 1977-05-03 | The Lubrizol Corporation | Method of rerefining oil by distillation and extraction |
US4154670A (en) * | 1975-11-24 | 1979-05-15 | The Lubrizol Corporation | Method of rerefining oil by dilution, clarification and extraction |
US4169044A (en) * | 1977-07-21 | 1979-09-25 | Phillips Petroleum Company | Re-refining used lube oil |
US4269698A (en) * | 1979-11-28 | 1981-05-26 | Edwards Oil Service, Inc. | Oil treatment processes, and products obtained thereby |
US4351718A (en) * | 1981-06-01 | 1982-09-28 | General Electric Company | Method for removing polyhalogenated hydrocarbons from nonpolar organic solvent solutions |
US4410422A (en) * | 1981-10-23 | 1983-10-18 | General Electric Company | Method for removing polyhalogenated hydrocarbons from nonpolar organic solvent solutions |
US4417977A (en) * | 1982-09-30 | 1983-11-29 | The Franklin Institute | Removal of PCBS and other halogenated organic compounds from organic fluids |
FR2539742B1 (en) * | 1983-01-24 | 1986-09-05 | Sanofi Sa | AMINO DERIVATIVES OF PYRIDAZINE SUBSTITUTED IN POSITION 6 BY A HETEROCYCLE OR ALICYCLE, SAID DERIVATIVES Being ACTIVE ON THE CENTRAL NERVOUS SYSTEM |
US4431524A (en) * | 1983-01-26 | 1984-02-14 | Norman George R | Process for treating used industrial oil |
AU555461B2 (en) * | 1983-03-10 | 1986-09-25 | Sea Marconi Decontamination S.R.L. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
US4532028A (en) * | 1983-10-24 | 1985-07-30 | Niagara Mohawk Power Corporation | Method for reducing content of halogenated aromatics in hydrocarbon solutions |
-
1988
- 1988-08-18 DE DE88DE8800501T patent/DE3890632D2/en not_active Expired - Lifetime
- 1988-08-18 JP JP63506882A patent/JPH02504523A/en active Pending
- 1988-08-18 US US07/466,262 patent/US5141628A/en not_active Expired - Fee Related
- 1988-08-18 EP EP88907226A patent/EP0377606B1/en not_active Expired - Lifetime
- 1988-08-18 WO PCT/DE1988/000501 patent/WO1989001508A1/en active IP Right Grant
- 1988-08-18 DE DE88907226T patent/DE3876245D1/de not_active Expired - Fee Related
- 1988-08-18 AU AU22697/88A patent/AU2269788A/en not_active Abandoned
-
1989
- 1989-02-22 CN CN89101848A patent/CN1021233C/en not_active Expired - Fee Related
-
1990
- 1990-02-16 RU SU904743108A patent/RU1834902C/en active
Non-Patent Citations (1)
Title |
---|
See references of WO8901508A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE3876245D1 (en) | 1993-01-07 |
JPH02504523A (en) | 1990-12-20 |
DE3890632D2 (en) | 1990-07-19 |
CN1021233C (en) | 1993-06-16 |
CN1045122A (en) | 1990-09-05 |
WO1989001508A1 (en) | 1989-02-23 |
US5141628A (en) | 1992-08-25 |
EP0377606B1 (en) | 1992-11-25 |
RU1834902C (en) | 1993-08-15 |
AU2269788A (en) | 1989-03-09 |
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