EP1141181A1 - Procede de retraitement d'huiles usees, huiles de base obtenues selon ce procede et utilisation de ces dernieres - Google Patents
Procede de retraitement d'huiles usees, huiles de base obtenues selon ce procede et utilisation de ces dernieresInfo
- Publication number
- EP1141181A1 EP1141181A1 EP99971836A EP99971836A EP1141181A1 EP 1141181 A1 EP1141181 A1 EP 1141181A1 EP 99971836 A EP99971836 A EP 99971836A EP 99971836 A EP99971836 A EP 99971836A EP 1141181 A1 EP1141181 A1 EP 1141181A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- oils
- distillation
- extraction
- waste
- 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
- 239000003921 oil Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000002199 base oil Substances 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000012958 reprocessing Methods 0.000 title claims abstract description 12
- 235000019198 oils Nutrition 0.000 claims abstract description 80
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004821 distillation Methods 0.000 claims abstract description 28
- 238000000605 extraction Methods 0.000 claims abstract description 28
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 238000005194 fractionation Methods 0.000 claims abstract description 8
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 3
- 239000008158 vegetable oil Substances 0.000 claims abstract description 3
- 239000010687 lubricating oil Substances 0.000 claims description 25
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000010913 used oil Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000002427 irreversible effect Effects 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 4
- 230000020477 pH reduction Effects 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 6
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 108010017739 LAGA Proteins 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- YJAGIIHSFUDVBG-OOEBKATBSA-N laga peptide Chemical compound C([C@H](NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H](C)NC(=O)[C@@H](NC(=O)[C@H](C)N)CC(C)C)C(=O)N[C@@H](CCC(=O)OC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)[C@H](CCC(=O)OC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@@H](N)CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](C)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H](C)N)C(=O)OC(=O)CC[C@H](NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)N)C(=O)N[C@@H](C)C(=O)OC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](N)CCC(O)=O)C1C=NC=N1 YJAGIIHSFUDVBG-OOEBKATBSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline 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
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
- C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
-
- 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
- C10M175/005—Working-up used lubricants to recover useful products ; Cleaning using extraction processes; apparatus therefor
Definitions
- the present invention relates to a process for the reprocessing of waste oils by distillation and extraction process, the base oils obtainable with the process and their use.
- waste products plays an increasingly important role today, in particular the removal of environmental pollutants such as halogenated hydrocarbons, aromatics and the like. These represent acute and latent threats to human health and other environmental protection goods such as water, soil, air, plants and animals. To assess the actual risk potential, material compositions and their concentrations must be examined and evaluated. This information serves as the basis for the type and scope of the disposal measures to be taken.
- Disposal can be carried out both by removing the contaminated products and by recycling them, although recycling is generally preferred. Recycling is generally possible in two ways: The product can be recycled, i.e. can be reprocessed, or it can be used as fuel for energy. Here certain criteria must be observed, which depend on the product and the respective pollution.
- waste oils are subject to the so-called waste oil ordinance (AltölV) dated
- Waste oils to be reprocessed are generally allowed a maximum paint value of 20 ppm poly chlorinated biphenyls (PCB) and a total halogen content of 0.2%. However, exceptions are possible, depending on the reprocessing process chosen.
- PCB poly chlorinated biphenyls
- step B) continuing distillation to obtain a distillate with substantially the viscosity of lubricating oil; C) extracting contaminants from the distillate of step B) with an organic liquid extractant which is substantially immiscible with the distillate and
- organic extractants are mentioned in particular: ethanol, diacetone alcohol, ethylene glycol mono (lower alkyl) ether, diethylene glycol, diethylene glycol mono (lower alkyl) ether, o-chlorophenol, furfural, acetone, formic acid, 4-butyrolactone, lower alkyl esters of lower mono- and dicarboxylic acids , Dimethylformamide, 2-pyrrolidone and N- (lower alkyl) -2-pyrrolidone, epichlorohydrin, dioxane, morpholine, lower alkyl and amino (lower alkyl) morpholines, benzonitrile and di- (lower alkyl) sulphoxides and phosphonates.
- Preferred extraction agents are ethylene glycol monomethyl ether, dimethylformamide or N-methyl-2-pyrrolidone. Furthermore, 20 to 50 parts by weight of extractant per 100 parts by weight of the distillate obtained from step B) are used in the extraction step C).
- the distillation should be carried out without a fractionation column or similar device.
- disruptive constituents can optionally be removed by means of a diluent in the form of an organic solvent, which can additionally be preceded by heating the waste oil with an aqueous, strongly alkaline solution.
- this process does not always lead to satisfactory results with regard to the quality of the refurbished oils, which still show excessive levels of pollutants after the refurbishment.
- the present invention is therefore based on the object of developing the method described at the outset in such a way that the base oils obtained have as low a level of pollutants as possible, such as aromatics and especially polycyclic, aromatic hydrocarbons. Furthermore, the procedure and the possible starting materials should be flexible. At the same time, good results should be achieved in the reprocessing process despite the high quality of the base oils to be obtained.
- the above object is achieved by a method for reprocessing used oils and producing high-quality base oils, comprising the following steps:
- step B) distilling the waste oil obtained after step A) under vacuum to separate off heating oil and diesel fractions with a boiling cut of about 170 to 385 ° C. in the form of high-quality heating oils;
- step C) Gentle distillation of the distillation residue from step B) by means of thin-film evaporation in a high vacuum to maintain a lubricating oil fraction with a customary viscosity range, which can be separated into boiling cuts of different viscosity levels by a subsequent distillation fractionation step, if necessary under vacuum;
- step D) If appropriate, gentle distillation of the bottom product from step C) to obtain a lubricating oil fraction of higher viscosity from the higher boiling range, which can be separated as required by a subsequent distillation fractionation step, if appropriate under vacuum;
- step C) Extracting the fraction or fractions in the form of lubricating oil fractions or boiling sections of different viscosity layers from step C) and optionally D) with N-methyl-2-pyrrolidone (NMP) and / or N-formylmorpholine (NMF) as an extractant for maintenance purposes high quality
- NMP N-methyl-2-pyrrolidone
- NMF N-formylmorpholine
- Base oils the extraction being carried out in such a way that undesired constituents are removed almost quantitatively and the content of polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) is in each case significantly below 1 mg / kg.
- PAH polycyclic aromatic hydrocarbons
- PCB polychlorinated biphenyls
- waste oil is to be understood to mean any used semi-liquid or liquid substance which is wholly or partly composed of mineral oil or synthetic oils, and any oil-containing residue, as well as water-oil mixtures or the like.
- waste oils suitable for reprocessing into lubricating oils, in particular used internal combustion engine and gear oils, mineral machine, turbine and hydraulic oils, including their synthetic and semi-synthetic components based on mineral hydrocarbons. The process according to the invention for reprocessing these waste oils is described in detail below:
- a first step A water and parts of low-boiling components, such as gasoline or solvent fractions, are distilled off. This is preferably done at normal pressure or under a slight vacuum (up to about 600 mbar) at a temperature of about 140 to 150 ° C.
- a concentrated, aqueous potassium hydroxide solution can optionally be used in a particularly advantageous manner in the process according to the invention. It is already used in this first stage in order not to burden the vacuum generation with the water to be separated from the potassium hydroxide solution in the subsequent distillation steps.
- the potassium hydroxide solution is preferably highly concentrated, in particular about 5 to 50% strength.
- step A) gives the concentration of the potassium hydroxide as a very homogeneously distributed, very concentrated and therefore very effective reagent for binding acidic constituents in the used oil, including extensive demetallization of the used oils.
- potassium hydroxide solution results in a particularly flowable and homogeneous distillation residue in the thin-layer evaporation described below in step C) due to the specific "soaps" that form.
- other alkalis such as, for example, the sodium compounds described in US Pat. No. 4,021,333, tend to precipitate and form lumps which considerably interfere with the further course of the process.
- the potency of the lubricating oil distillates can be further improved by the use of potassium hydroxide solution, and further advantages with regard to the procedure and chemical effect are achieved in the subsequent extraction.
- This type of alkaline treatment also eliminates the need for a further step to mechanically separate solid precipitates.
- the fuel oil and diesel fractions present with a boiling cut of about 170 to 385 ° C. in step B) are removed from the waste oil by distillation in vacuo.
- the residue obtained in this way is subjected to gentle thin-layer evaporation in a high vacuum after step C), in which the actual lubricating oil fraction is obtained. To achieve the desired viscosity layers, these can then be fractionated again.
- step D) The residue from the thin film evaporation (bottom product) still contains highly viscous and very valuable lubricating oil components, which can be obtained in step D) by gentle distillation, such as a subsequent second thin film evaporation - at correspondingly higher distillation temperatures or lower pressure - and also fractionated if necessary.
- step D) is not always necessary, but when used it improves the yield of base oils and thus the economy of the process.
- NMP N-methyl-2-pyrrolidone
- NMF N-Formylmorpholine
- the lubricating oils or fractions from steps C) and D) can be individually processed further or even partially combined and only then further processed.
- the extraction can preferably be carried out in a column (sieve tray, packing).
- the countercurrent process is preferred.
- the use of fillers is more robust with regard to the process control as well as advantages with regard to the possible throughputs (volume flows) and the extractant distribution of NMP or NMF in the oil.
- the NMP / oil or NMF / oil supply Ratio is between 0.5 and 2.0 (v / v) depending on the requirements for the qualities of the base oils to be produced.
- the extraction can be carried out in the temperature range of about 20 to 90 ° C.
- the procedure is possible using a temperature gradient in the column.
- the temperatures are about 50 to 90 ° C at the top of the column (raffinate outlet) and about 10 to 50 ° C at the bottom of the column (extract outlet).
- the advantage here is the higher selectivity of the extractant (for example NMP) at lower temperatures, so that base oil components dissolved in the extractant are redissolved, while the unwanted components to be removed remain in solution. This can ultimately lead to a significant increase in refined base oil yield.
- the NMP and / or NMF present in the raffinate phase and the extract is recovered in the usual way by subsequent distillation processes and returned to the process.
- an alkalinity reserve is created in the oil feed (feed) for extraction, which prevents the otherwise irreversible formation of acidic reaction products of the extractant.
- PAH polycyclic aromatic hydrocarbons
- PCB polychlorinated biphenylene
- the invention also relates to the base oils obtainable by the process described above.
- base oil qualities with color values according to ASTM between 0.5 and 3.0 are obtained.
- the neutralization number (abbreviated as NZ) as a measure of residual acidic constituents in the base oil is between 0.01 and 0.03 mg KOH / g.
- the extraction increases the viscosity index (abbreviated as VI) by 6 to 10 points. It is noteworthy that the viscosity index of these lubricating oil distillates is significantly higher than that of conventional base oil based on the presence of synthetic oil (polyalphaolefins (PAO), hydrocracked oils (HC oils)).
- PAO polyalphaolefins
- HC oils hydrocracked oils
- the process according to the invention significantly reduces the aromatic content (abbreviated as CA) in the base oil.
- CA aromatic content
- polycyclic aromatic hydrocarbons are almost completely quantitatively removed (PAH according to Grimmer - sum of a specified number of individual substances ⁇ 1 mg / kg, benzo (a) pyrene ⁇ 0.1 mg / kg).
- PAH polycyclic aromatic hydrocarbons
- benzo (a) pyrene ⁇ 0.1 mg / kg.
- Waste oils processed according to the method according to the invention with the above-mentioned high PCB contents show a PCB content in the base oils obtained according to the invention which is below the limit of determination of the analysis method. This is also important insofar as both the national and the European regulations regarding the processing of waste oils contaminated in this way explicitly only allow such processes in individual cases if the high quality standards for the obtained base oil can be achieved.
- the method according to the invention fulfills these requirements.
- used oils containing vegetable oils so-called biodegradable oils
- biodegradable oils can also be reprocessed. Up to about 5% of such oils can be present in the waste oil without affecting the quality of the base oil.
- the base oils obtained can be used in a variety of ways, for example as starting products for lubricants or for products in the petrochemical sector, since there are no restrictions due to the excellent quality within the scope of the invention.
- the advantages associated with the invention are complex.
- the process according to the invention is far superior to the customary methods of bleaching earth treatment, chemical treatment or hydrogenation, and also the known distillation processes from the prior art.
- the process according to the invention can thus be carried out without waste, since the extracting agent NMP or NMF can be recovered and reused, and the extract is used as heating oil or as a heating oil equivalent.
- bleaching earth contaminated with oil remains in the bleaching earth process, and during the hydrogenation the exhausted catalysts must be disposed of and the reaction gases (H_S, HC1) rendered harmless.
- the energy balance according to the method of the invention is very favorable. You can work almost without pressure. Only in order to overcome the internal fluid friction and the pipe resistance during transport are pressures in the range of max. 5 bar necessary. The maximum temperature range is 230 ° C to ensure the recovery of the extractant for its reuse. In other processes, refining effects only occur at temperatures between 290 and 300 ° C (bleaching de process), or high pressures must also be used (hydrogenation: temperatures up to 350 ° C and operating pressures between 30 and 200 bar).
- the method according to the invention also offers advantages with regard to occupational safety, since the extraction agents NMP or NMF are classified as non-toxic (classification as Xi: irritant according to GefStoffV, with hazard class A III, WGK 1).
- NMP or NMF are classified as non-toxic (classification as Xi: irritant according to GefStoffV, with hazard class A III, WGK 1).
- Xi irritant according to GefStoffV, with hazard class A III, WGK 1
- H2S is also formed as a highly toxic gas and hydrogen chloride as a very corrosive gas.
- the base oil quality that can be achieved with the invention, as is achieved by the NMP or NMF extraction.
- the base oils have extremely good color values, a low neutralization number (NZ) and a high viscosity index (VI).
- the aromatic content in the base oil is significantly reduced by the process according to the invention.
- polycyclic aromatic hydrocarbons (PAHs) are removed almost quantitatively (total PAH according to Grimmer ⁇ 1 mg / kg, benzo (a) pyrene ⁇ 0.1 mg / kg).
- the content of polychlorinated biphenyls (PCB) in the base oil obtained is also below the limit of quantification.
- the bleaching earth process achieves poorer color values, an unpleasant smell, a significantly higher NZ, a lower VI, a significantly poorer aging behavior and inadequate removal of polycyclic aromatic hydrocarbons.
- Hydrogenation processes offer better yields with a lower viscosity index (VI) and otherwise comparable values, but quantitative removal of polycyclic aromatic hydrocarbons is only possible under extreme hydrogenation conditions and the use of precious metal catalysts, which are not common in the practice of lubricating oil-base oil production .
- VI viscosity index
- Waste oil according to waste oil V is distilled with the addition of 0.5% of a 50% potassium hydroxide solution in a plant under a vacuum of 600 mbar in a temperature range of 140 ° C for the purpose of aborting the water and the low boilers.
- the dry oil obtained is freed from the middle distillate cut at the boiling point of 380 ° C. in a subsequent middle oil distillation at a vacuum of 60 mbar and a temperature in the bottom of the column of 260 ° C.
- the bottom product of the middle oil distillation column passes into a thin-layer evaporation, in which, under a vacuum of 3 mbar and a heat transfer oil temperature of 384 ° C, the feeds into a lubricating oil distillate mixture and a bottom product.
- the lubricating oil distillate mixture is separated in a subsequent fractionation into two boiling sections under the process conditions 80 mbar and 280 ° C distillation temperature.
- the oil (feed) used is countercurrent to the solvent NMP used.
- the undesired constituents, among other things, the polycyclic aromatic hydrocarbons dissolve from the feed used while at the same time improving the quality of the lubricating oil distillate used.
- the Rafmat-NMP mixture emerging at the top of the column is then fed to an NMP solvent recovery unit in order to reuse this solvent in the process.
- the obtained lubricating oil distillate or lubricating oil refinate of the respective viscosity level V40 either 20 mm 2 / s or 36 mm 2 / s is then used for the formulation of new lubricating oils, such as engine oils, gear oils, hydraulic oils and other purposes.
- the extract obtained also passes through a solvent recovery system in order to be able to recover the solvent NMP from the extract for a new use.
- the extract obtained can be used as heating oil or as a heating oil blend in heating oil mixtures.
- the bottom product from thin-film evaporation is subjected to a further distillation in a subsequent further thin-film evaporation stage at a higher vacuum - 0.1 mbar and a temperature of 410 ° C.
- a separation into a highly viscous lubricating oil fraction with a viscosity of 253 mm 2 / s and a still remaining residue takes place, which is used as a heating oil admixture component, for example as a reducing agent. tion oil in heating oil mixtures for steel production.
- the highly viscous lubricating oil distillate obtained is also subjected to a subsequent selective refining with NMP (extraction), the reaction conditions in the column being operated isothermally at 90 ° C.
- the properties of the base oil obtained are as follows:
- the base oils obtained have extraordinarily good color values, low neutralization numbers (NZ) and a high viscosity index (VI).
- the aromatic content is reduced significantly in each case, the polycyclic aromatic hydrocarbon (PAH) content is well below 1 mg / kg and the benzo (a) pyrene content can be reduced to below 0.1 mg / kg.
- the polychlorinated biphenylene (PCB) content was below the detection limit of the analytical method. As a result, the base oils obtainable with the invention are of excellent quality.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Fats And Perfumes (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19852007A DE19852007C2 (de) | 1998-11-11 | 1998-11-11 | Verfahren zur Wiederaufarbeitung von Altölen |
DE19852007 | 1998-11-11 | ||
PCT/EP1999/008667 WO2000027957A1 (fr) | 1998-11-11 | 1999-11-11 | Procede de retraitement d'huiles usees, huiles de base obtenues selon ce procede et utilisation de ces dernieres |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1141181A1 true EP1141181A1 (fr) | 2001-10-10 |
EP1141181B1 EP1141181B1 (fr) | 2004-02-11 |
Family
ID=7887428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99971836A Expired - Lifetime EP1141181B1 (fr) | 1998-11-11 | 1999-11-11 | Procede de retraitement d'huiles usees |
Country Status (19)
Country | Link |
---|---|
US (1) | US6712954B1 (fr) |
EP (1) | EP1141181B1 (fr) |
JP (1) | JP4246397B2 (fr) |
CN (1) | CN1185327C (fr) |
AT (1) | ATE259405T1 (fr) |
AU (1) | AU1161900A (fr) |
BR (1) | BR9916606B1 (fr) |
CA (1) | CA2351606C (fr) |
CZ (1) | CZ298571B6 (fr) |
DE (2) | DE19852007C2 (fr) |
DK (1) | DK1141181T3 (fr) |
ES (1) | ES2222051T3 (fr) |
HU (1) | HU226925B1 (fr) |
PL (1) | PL191398B1 (fr) |
PT (1) | PT1141181E (fr) |
RU (1) | RU2217484C2 (fr) |
SK (1) | SK285213B6 (fr) |
UA (1) | UA69426C2 (fr) |
WO (1) | WO2000027957A1 (fr) |
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CA2396206A1 (fr) * | 2002-07-30 | 2004-01-30 | Nouredine Fakhri | Methode de traitement d'huiles usees |
JP2004210945A (ja) * | 2002-12-27 | 2004-07-29 | Toshiba Corp | 芳香族ハロゲン化合物の分離方法 |
US8366912B1 (en) | 2005-03-08 | 2013-02-05 | Ari Technologies, Llc | Method for producing base lubricating oil from waste oil |
US7529741B2 (en) * | 2006-03-06 | 2009-05-05 | Veveo, Inc. | Methods and systems for segmenting relative user preferences into fine-grain and coarse-grain collections |
EP1847587B1 (fr) * | 2006-04-18 | 2010-05-26 | Horst Fuhse | Procédé de traitement d'huiles usées pour obtenir des huiles de base à haut indice de viscosité |
ES2303447B1 (es) * | 2006-07-27 | 2009-06-12 | Juan Flores Velazquez | Procedimiento de regeneracion de aceites minerales usados y residuos asfalticos por extraccion liquido / liquido y producto asi obtenido. |
US20090038692A1 (en) * | 2007-08-09 | 2009-02-12 | 21St Century R & D, Llc | Modification of vegetable oils for fuel applications |
US20110139106A1 (en) * | 2007-08-09 | 2011-06-16 | 21St Century R & D, Llc | Modification of fats and oils for fuel and lubricating applications |
DE102007051373B4 (de) * | 2007-10-26 | 2010-11-11 | Hii-Gmbh - Industrianlagen - Bau Und Beratung | Verfahren und Vorrichtung zur Gewinnung von Diesel oder Heizöl aus kohlenwasserstoffhaltigen Rückständen |
WO2011074623A1 (fr) * | 2009-12-18 | 2011-06-23 | Kato Eisaku | Procédé de production d'huile récupérée |
CN102373108B (zh) * | 2010-08-18 | 2013-09-25 | 北京金隅红树林环保技术有限责任公司 | 一种废润滑油再生基础油的工艺方法 |
CN102604732A (zh) * | 2012-02-14 | 2012-07-25 | 安徽国孚润滑油工业有限公司 | 再生基础油n-甲基吡咯烷酮静态混合旋流分离抽提工艺 |
WO2014135966A1 (fr) * | 2013-03-07 | 2014-09-12 | Verolube, Inc. | Procédé et appareil pour la récupération d'huiles synthétiques à partir de courants huileux composites |
US9394495B1 (en) | 2013-09-18 | 2016-07-19 | Thomas George Murray | Post hydrotreatment finishing of lubricant distillates |
MX2016005893A (es) * | 2013-11-08 | 2016-08-17 | Sener Ing & Sist | Proceso para aumentar el rendimiento de bases lubricantes en la regeneracion de aceites usados. |
GB2521133A (en) * | 2013-12-10 | 2015-06-17 | Wei-Ming Chang | Method for desulfurization and aromatic compound removal of re-refined base oil that is recovered from waste lubricating oil |
CN104479736A (zh) * | 2014-12-03 | 2015-04-01 | 烟台市牟平区留德润滑油销售有限公司 | 一种废润滑油馏分油精制方法 |
CN104893767B (zh) * | 2015-05-19 | 2016-08-17 | 李菊明 | 一种废机油加工高品质燃料油的生产工艺 |
US10881984B2 (en) * | 2015-11-10 | 2021-01-05 | Hindustan Petroleum Corporation Limited | Composition and a process for reducing aromatics from a hydrocarbon feedstock |
ES2629851B1 (es) * | 2016-02-15 | 2018-04-25 | José Antonio GÓMEZ MIÑANA | Procedimiento de triple destilación para la regeneración de aceites usados incluyendo tratamiento cáustico en línea en la segunda destilación |
CN105797568B (zh) * | 2016-05-18 | 2018-11-23 | 湖南省小尹无忌环境能源科技开发有限公司 | 一种利用废有机溶剂制复合脱硝剂的方法 |
US9920262B1 (en) * | 2016-11-22 | 2018-03-20 | Rj Lee Group, Inc. | Methods of separation of pyrolysis oils |
CN107699331B (zh) * | 2017-09-18 | 2020-07-28 | 武汉工程大学 | 一种废润滑油分级除杂的净化方法 |
CN108085121A (zh) * | 2017-12-22 | 2018-05-29 | 常州菲纳斯能源科技有限公司 | 废润滑油再生及回收芳烃的处理方法 |
CN109701509B (zh) * | 2019-02-19 | 2023-08-08 | 安徽国孚凤凰科技有限公司 | 一种硅胶吸附抽提再生基础油后的再生装置及方法 |
KR102085351B1 (ko) * | 2019-07-08 | 2020-03-05 | 이종호 | 폐유를 이용한 연료유의 제조방법 |
CN113061481A (zh) * | 2021-03-27 | 2021-07-02 | 刘新华 | 一种废矿物油的回收净化再生利用工艺 |
CN114854484B (zh) * | 2022-06-02 | 2023-04-25 | 河北车迪石油化工有限公司 | 废矿物油再生工艺及系统 |
CN115353928A (zh) * | 2022-08-19 | 2022-11-18 | 唐亮 | 基于化学法处理的再生润滑油 |
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IT1154554B (it) * | 1982-11-11 | 1987-01-21 | D E L Co Di Coppo Mario | Procedimento per il disinquinamento di oli minerali in genere e di fluidi siliconici dielettrici |
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DE3723607A1 (de) | 1987-07-17 | 1989-01-26 | Ruhrkohle Ag | Verfahren zum hydrierenden aufarbeiten von altoelen |
FR2725725B1 (fr) * | 1994-10-17 | 1996-12-13 | Inst Francais Du Petrole | Procede et installation pour la purification des huiles usagees |
US6117309A (en) * | 1997-09-08 | 2000-09-12 | Probex Corporation | Method of rerefining waste oil by distillation and extraction |
-
1998
- 1998-11-11 DE DE19852007A patent/DE19852007C2/de not_active Expired - Lifetime
-
1999
- 1999-11-11 JP JP2000581124A patent/JP4246397B2/ja not_active Expired - Lifetime
- 1999-11-11 PL PL348757A patent/PL191398B1/pl unknown
- 1999-11-11 UA UA2001063912A patent/UA69426C2/uk unknown
- 1999-11-11 AU AU11619/00A patent/AU1161900A/en not_active Abandoned
- 1999-11-11 BR BRPI9916606-2A patent/BR9916606B1/pt not_active IP Right Cessation
- 1999-11-11 CZ CZ20011559A patent/CZ298571B6/cs not_active IP Right Cessation
- 1999-11-11 AT AT99971836T patent/ATE259405T1/de active
- 1999-11-11 HU HU0104072A patent/HU226925B1/hu unknown
- 1999-11-11 ES ES99971836T patent/ES2222051T3/es not_active Expired - Lifetime
- 1999-11-11 CA CA002351606A patent/CA2351606C/fr not_active Expired - Lifetime
- 1999-11-11 DK DK99971836T patent/DK1141181T3/da active
- 1999-11-11 PT PT99971836T patent/PT1141181E/pt unknown
- 1999-11-11 US US09/831,104 patent/US6712954B1/en not_active Expired - Lifetime
- 1999-11-11 DE DE59908537T patent/DE59908537D1/de not_active Expired - Lifetime
- 1999-11-11 RU RU2001116108/04A patent/RU2217484C2/ru active
- 1999-11-11 WO PCT/EP1999/008667 patent/WO2000027957A1/fr active IP Right Grant
- 1999-11-11 SK SK636-2001A patent/SK285213B6/sk not_active IP Right Cessation
- 1999-11-11 EP EP99971836A patent/EP1141181B1/fr not_active Expired - Lifetime
- 1999-11-11 CN CNB998131733A patent/CN1185327C/zh not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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See references of WO0027957A1 * |
Also Published As
Publication number | Publication date |
---|---|
HUP0104072A3 (en) | 2004-08-30 |
PL191398B1 (pl) | 2006-05-31 |
SK285213B6 (sk) | 2006-09-07 |
PT1141181E (pt) | 2004-06-30 |
AU1161900A (en) | 2000-05-29 |
DK1141181T3 (da) | 2004-06-14 |
CN1326498A (zh) | 2001-12-12 |
HU226925B1 (en) | 2010-03-01 |
PL348757A1 (en) | 2002-06-03 |
WO2000027957A1 (fr) | 2000-05-18 |
CA2351606A1 (fr) | 2000-05-18 |
CZ20011559A3 (cs) | 2001-12-12 |
DE59908537D1 (de) | 2004-03-18 |
DE19852007A1 (de) | 2000-05-18 |
DE19852007C2 (de) | 2002-06-13 |
BR9916606A (pt) | 2001-08-14 |
ES2222051T3 (es) | 2005-01-16 |
ATE259405T1 (de) | 2004-02-15 |
EP1141181B1 (fr) | 2004-02-11 |
CA2351606C (fr) | 2005-06-07 |
CZ298571B6 (cs) | 2007-11-07 |
SK6362001A3 (en) | 2001-11-06 |
JP4246397B2 (ja) | 2009-04-02 |
CN1185327C (zh) | 2005-01-19 |
JP2002529579A (ja) | 2002-09-10 |
RU2217484C2 (ru) | 2003-11-27 |
BR9916606B1 (pt) | 2011-10-18 |
US6712954B1 (en) | 2004-03-30 |
HUP0104072A2 (hu) | 2002-05-29 |
UA69426C2 (en) | 2004-09-15 |
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