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
  • C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
• • 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
• • 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

Definitions

• the present invention concerns a high-yield and low-pollutio process to re-refine used lubricating oils.
• re-refining means transforming used oils and fats derived from engines or from other industrial uses - into base oils.
• Su base oils are then used, after mixing with suitable additives, as n lubricating oils having qualitative features which can be fully compar to those of the oils directly obtained by petroleum refinery.
• the sulphuric acid process was the first one to be conceived an adopted, but is now being dropped due to the considerable pollution pro ⁇ blems which it involves. Said process essentially comprises the followin steps, as shown on the block diagram of fig. 1:
• Fig. 1 also indicates the fluid masses flowing into and out of eac single block, with reference to an inlet flow-rate of used oils Al equa to 100. This shows that the final yield of the sulphuric acid proces does not even reach 60 .
• composition of sai sludges is in fact quite varied and includes - besides sulphuric acid an the hydrocarbon compounds - polymeric compounds with high molecula weight, organic and inorganic compounds of sulphur, chlorine, nitroge and phosphorus, and heavy metals as chromium, copper, zinc, iron, nicke and lead.
• Said hydrocarbon can in fact be easily liquefied and has, in this liquid phase, a very low density.
• propane thus acts thereon as a thinning and fluidizing agent, allowing to easily obtain the separation of a first liquid fraction Bl with high viscosity, containing the high polymers and heavy metals - generally indicated by "asphalts" - from a second liquid fraction B2 consisting exclusively of the clarified and dehydrated oils.
• the plant of course provides for a depropanizing treatment of the liquid fraction B2, and for the recycle of the propane thus recovered.
• the successive filtration step C with decolorant earths Cl is car ⁇ ried out with a hot treatment so that, as well as recovering the exhaust ⁇ ed earths C2, one also recovers a gaseous fraction C3 consisting of a minor portion of the gas oil contained in B2. The remaining part of gas oil abandons this block together with the decolorized oils C4 and is recovered in Dl in the successive distillation step D.
• the distillation step D and the final decolorization step E are fully identical to those previously described with reference to the sulphuric acid process.
• the propane process represents a considerable improvement in res ⁇ pect of the sulphuric acid process, both as far as yield - which has risen to about 68 - and as far as pollution, which is notably reduced. Nevertheless, also this process has some inconveniences.
• the handling of propane creates problems of safety for the workers on account of its high explosiveness; furthermore, in spite of the above mentioned depropanizing treatments, the heavy fraction of asphalts Bl still shows traces of propane. This even small quantity of propane is sufficient to prevent the use of such asphalts in potentially interesting fields as the roadway or the building field.
• the asphalts should be consi ⁇ dered in every respect as a waste product, which can be disposed of - b previous dilution with gas oil so as to make it sufficiently fluid - onl as fuel having a good heat value but a high pollution rate.
• a typical us thereof is in the casehardening furnaces, already provided with specia equipment to depurate the smokes and apt to eliminate also the pollutant present in such asphalts.
• the light vaporizable fraction o In contact with the column wall, the light vaporizable fraction o the oils instantly turns into a gas phase, while the heavy fraction stay liquid and collects onto the bottom of the column. The vaporized fractio is then collected and fractionated into the desired cuts in a successiv fractionating column.
• the inventors of the present patent have thus proposed to themsel ves the object of preparing a process to re-refine used oils: allowing t reduce or fully abandon the use of reagents which are difficult to elimi nate or anyhow harmful for the environment or dangerous for human safety; apt to be carried out with a simple and compact plant, not weighing o the production costs and also allowing to reduce energy consumption; ap to be carried out in a completely static plant, the single components o which should not include any moving parts, highly subject to great foul ing problems typical of the used oil treatments; and, finally, apt t increase the still not satisfactory yields of the known processes, bot for what concerns the quantity and quality of the recovered oils, and fo what concerns the possibility to utilize the by-products in economicall profitable uses, apt to make said process globally more advantageous.
• said objects are reached with process to re-refine used oils - of the type in which said oils are sub jected to a first preflash treatment to eliminate the water and the mos volatile fractions contained therein, to a purification treatment to eli minate the high polymers and heavy metals, to a fractional distillatio treatment to obtain one or more oil fractions for use as lubricatin bases, and finally to a decolorization treatment - characterized in that:
• - said purification treatment is carried out in three successiv steps: a first step of pretreatment wherein, before said preflash treat ment, a highly basic reagent is added and mixed with the oils; a secon step wherein, before the fractional distillation treatment, the oil resulting from the preflash treatment are decanted; a third step where a heavy liquid fraction containing said high polymers and heavy metals discharged from the base of said fractionating column.
• Fig. 1 is a block diagram, illustrating the known-type sulphur acid re-refining process
• Fig. 2 is a block diagram, illustrating the known-type propane r refining process
• Fig. 3 is a block diagram, illustrating the process to re-refi used oils according to the present invention
• Fig. 4 is a diagram of the plant to carry out the process of t invention, wherein the basic reagent addition step and the preflash st are illustrated in further detail;
• Fig. 5 is a diagram of the plant to carry out the process of t invention, wherein the fractional distillation step and the step separate the heavy fraction containing the high polymers and heavy meta are illustrated in further detail.
• the process to re-refine used oils, according to the present inve tion differs from the known processes for the fact of having notab simplified the purification treatment and of having combined into a si gle column all the distillation treatments (which, in the known proces es, are carried out into several cascade columns) as well as the oper tion to separate a heavy fraction containing the high polymers and hea metals. Moreover, this last separation is carried out by means of cyclone device positioned in the lower part of the distillation colum which does not provide for the use of any movable parts and is therefo not subject to problems of fouling or blocking, caused by the high visc sity and the special composition of the materials being treated. Fig.
• FIG. 3 reports a block diagram illustrating the main steps of th process according to the invention. Like the similar diagrams of figs. and 2 - illustrating the known processes and already discussed heretofor - this diagram indicates the fluid masses flowing into and out of th single blocks, with reference to a feeding flow-rate of used oils A equal to 100.
• the treatment to purify the used oils from the hi polymers and heavy metals includes a pretreatment A with a basic reagent
• a reagent preferred for this purpose is NaOH, which is added in A2 an mixed with the oils Al before the preflash treatment.
• Said pretreatmen does not act directly on the above pollutants, but helps on one hand t saponify the fatty acids present therein, favouring their precipitation and on the other hand to neutralize the chlorine present both in boun and in free form.
• the saponification of the fatty acids besides facili tating their elimination by decantation - hence improving the flowabilit of the system - destroys their volatility and thus prevents said acid from turning into vapour in the distillation column, thereby pollutin the oils both directly and with the polluting parts eventually boun thereto.
• the neutralization of chlorine also preserves the plant fro dangerous phenomena of corrosion, lengthening its working life.
• the successive preflash treatment B involves - as in the processe of known technique - the separation of an oily water flow Bl and a ga oil flow B2. Before being sent to the successive step, the flow of deh drated oils B3 resulting from the preflash treatment is left to rest fo a length of time sufficient to obtain the decantation of the saponifie or flocculate parts.
• the flow of oils, thus treated, is sent to a treatment of therma deasphalting and of fractional distillation C which simultaneously invol ves, both the separation of a light phase Cl containing gas oil and of heavy phase C2 containing the high polymers and heavy metals, and th fractionation of the oils into three cuts C3 of different density.
• Th three cuts thus obtained, suitably purified with a stripping treatment are sent to the final decolorization treatment D - known per se - int which is fed a flow of decolorant earths Dl and from which the flow o exhausted earths D2 is removed, thereby obtaining a main flow of re-refi ned oils D3, with a very high yield equal to about 7 .
• the yield can even rise to 75%-
• the decolorizatio of the re-refined oils D3 can be carried out with a hydrogen treatment also perfectly known in technique.
• Fig. 4 reports the blocks A and B.
• the used oils Al are fed throug the pump 1 into the preflash column 2.
• the basic reagent A2 with a flow-rate controlled by the meter ing pump 3-
• said reagent preferably consists of NaO and is added, as a 30% solution, in an amount such as to settle the pH o the used oils - at the outlet of column 2 - at a value between 10 and 13 and preferably between 11.8 and 12.2.
• the flow-rate of the pump 3 is thu preferably regulated automatically by a pH control device 4 positioned a the outlet of column 2.
• the used oils Al and the reagent A2 are then thoroughly mixed int a line mixer 5, and are subsequently preheated to a temperature of abou 120°-140°C into the exchanger 6 fed by the steam line VAP.
• the preflash column 2 is kept under a moderate vacuum degree, equa to about 200 mmHg, by means of an ejector 7 fed by the same steam li VAP.
• the flow A3 fed into column 2 is then separated into a vapour phas containing water and gas oil, and into a liquid phase, containing t dehydrated oils and the pollutants.
• the vapour phase is condensed by t water-cooled condenser 8a and sent to the gravity separator 9>
• the sa separator also receives the steam let out from the ejector 7 , after has been condensed in the condenser 8b.
• the separator 9 provides to separate an incondensable gaseous pha GAS - which is sent to a high-temperature burner, so as to destroy a gaseous pollutants present therein - from the two already described li quid flows Bl and B2.
• the water flow Bl slightly oil-polluted, is sen to a biological depuration plant together with the process waters let o of the other parts of the plant. This is actually the only waste produc of the process according to the present invention, which does not excee 4% by weight of the feeding and which creates no particular problems fo its proper elimination.
• the gas oil B2 - of excellent quality, seen tha the oils have not been subjected to treatments with polluting reagents can be introduced in the normal trade channel of fuels.
• the bottom product B3 of the column eventually condensed by cooling coil 10, is sent by a pump 11 into a collection tank 12.
• the di mensions of the tank 12 and the positioning of the inlet and outlet pipe are calculated so that the stay time therein of the flow B3 is at leas 48 hours.
• the saponified fatty acids and the other floccula te parts - thanks to the treatment with NaOH - are able to decant on th bottom of the tank 12, from which they are periodically removed throu the drain 13, entraining therewith a certain amount of impurities.
• Fig. 5 illustrates the thermal deasphalting and fractional distil lation treatments carried out on the flow B3 of dehydrated oils.
• Sai oils are first of all heated to a temperature of about 36 ⁇ °C in the me thane gas furnace 20.
• the oils are then fed to the bottom of the fracti nating column 21, into which is kept a vacuum degree of at least 10-2 mmHg (at the top of the column), thanks to a main ejector 22a, seri connected to two secondary ejectors 22b and 22c, all fed by the VAP lin
• the heated and partially vaporized oils are sent to t top of a cyclone device 23, positioned in the lower part of the column and consisting of an open-spiral channel leading down around a lar central tube which connects the bottom part of the column to its pa immediately above.
• the flow B3 almost totally vaporizes a the cyclone device 23 allows a perfect and complete separation of th gaseous phase from the liquid phase, which contains the very heavy oi fractions and all the pollutants consisting of the high polymers heavy metals.
• This liquid phase C2 commonly called “asphalts" is s to the collection tanks through a pump 24.
• the vapour phase released from the cyclone 23, moves up along column 21, meeting four successive filling packs 25, positioned o respective collection plates 26, which allow - in known manner - to through the vapour phase which rises towards the top, and to retain liquid which has condensed.
• the fractionating column 21 of the pres invention has been conceived so as to allow cutting the inlet flow int head fraction, substantially containing the process vapour and the oil, and into three intermediate cuts (indicated by C3/I, C3/II C3/IH) of re-refined oils of different density, ready for the differ commercial uses, as well as into the already described tail fraction C
• the filling should have a very low f resistance (5-10 mm Hg at most, for each pack) and a high gas/liq contact surface.
• An extremely positive result has been obtained by us a metal filling consisting of side-by-side, superposed, accordion-fol metal sheets, forming zig-zag channels allowing the vapours to rise, average size from 1 to a few centimeters.
• a filling of this type, m from stainless steel, is produced by Glitsch Italiana - Campoverde Aprilia (Latina), Italy - and is known on the market under the trade n GEMPACK.
• the liquid cut collected on the top plate 26a, namely the pl positioned under the first filling pack 25, is reflowed by the pump into a column zone just below said plate and, after having been coo into the water exchanger 28, it is sent to the head of the column 21. portion exceeding the requirement of the reflux is collected in C1, gas oil, to be put on the market together with the flow B2 separated the previous preflash step.
• the portion of these liquid cuts exceeding the reflux requirements are sent to separate part of a stripping column 29 formed of three different sections, into one o which also flows directly the cut collected on the bottom plate 26d. I the three sections of the stripping column 29 the three cuts are purifie even further, in a countercurrent of steam fed from the VAP line an superheated in the furnace 20.
• the flows coming from the main ejector 22a and from the secondar ejectors 22b and 22c, containing process vapour, incondensable gases an gas oil vapours, are condensed into the water condensers 32 and then col lected into a gravity phase separator 33-
• the ga oil phase escaped from the head of the column 21 is separated from th process water phase and from the incondensable gases.
• the gas oil is fe in Cl; the water flow 34 is recycled to the steam production boiler after having possibly undergone a depollution treatment; while the incon densable gases are sent into GAS and then into a combustion furnace t eliminate any possible polluting gases.
• the asphalt flow C2 - thanks to the total absence of solvents an for the very fact of containing, as vehicle of the pollutants, a fractio of very heavy and viscous oils (bright stock) - can be marketed, in a economically interesting way, to form bituminous roadbeds, to which i confers special elastomeric and deadening characteristics.
• the process to re-refine used oils according to the present inven tion is thus particularly advantageous compared to the processes of know technique.
• waste products of the process merely consist of t water separated from the oils in the preflash step. Said water forms very small fraction - about 4% - of the initial feed Al, and anyh creates, as seen above, no ecological problems as far as disposal concerned.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Fats And Perfumes (AREA)
• Lubricants (AREA)

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• 1992
  • 1992-09-30 IT ITMI922271A patent/IT1255534B/it active IP Right Grant
• 1993
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  • 1993-09-26 EG EG62393A patent/EG20181A/xx active
  • 1993-09-28 AT AT93921862T patent/ATE180009T1/de active
  • 1993-09-28 HU HU9401725A patent/HU213650B/hu unknown
  • 1993-09-28 WO PCT/EP1993/002628 patent/WO1994007798A1/en active IP Right Grant
  • 1993-09-28 CZ CZ19941579A patent/CZ287418B6/cs not_active IP Right Cessation
  • 1993-09-28 RU RU9494028710A patent/RU2099397C1/ru active
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  • 1993-09-28 ES ES93921862T patent/ES2132258T3/es not_active Expired - Lifetime
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• 1995
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• 1998
  • 1998-12-22 HK HK98114602A patent/HK1013280A1/xx not_active IP Right Cessation
• 1999
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