(19)

& 
(11) EP 1 712 608 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C10M 175/02 (2006.01)
26.08.2009 Bulletin 2009/35
(86) International application number:
(21) Application number: 04766956.9 PCT/ES2004/000418

(22) Date of filing: 23.09.2004 (87) International publication number:

WO 2005/028600 (31.03.2005 Gazette 2005/13)

(54) METHOD FOR REGENERATING USED OILS BY DEMETALLIZATION AND DISTILLATION

ALTÖLREGENERATIONSVERFAHREN MIT DEMETALLISATION UND DESTILLATION
PROCEDE DE REGENERATION D’HUILES USEES PAR DEMETALLISATION ET DISTILLATION

(84) Designated Contracting States: (72) Inventor: ANGULO ARAMBURU, Jeronimo

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR E-28760 TRES CANTOS (Madrid) (ES)
HU IE IT LI LU MC NL PL PT RO SE SI SK TR
(74) Representative: Carpintero Lopez, Francisco
(30) Priority: 23.09.2003 ES 200302203 Herrero & Asociados, S.L.
Alcalá 35
(43) Date of publication of application: 28014 Madrid (ES)
18.10.2006 Bulletin 2006/42
(56) References cited:
(73) Proprietor: Sener Grupo de Ingeniería, S.A. ES-T3- 2 124 879 ES-T3- 2 125 208
28760 Tres Cantos (Madrid) (ES) ES-T3- 2 169 748 FR-A1- 2 552 098
US-A- 3 930 988 US-A- 6 117 306
EP 1 712 608 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 712 608 B1

Description

FIELD OF THE INVENTION

5 [0001] The invention, in general, is associated with the regeneration of used oils; an industrial operation which consists
in recovering the base oils by separating them from the additives, from their degradation products and from the contam-
inants acquired during its use or collection. More specifically, the invention refers to a method for regenerating used
petroleum oils by demetallization and distillation.
[0002] The refined petroleum oils which are used to make lubricants and other industrial oils are called lubricant bases.
10 [0003] The lubricants and other industrial oils are formulated by mixing the lubricant bases with additives, some of
which contain metals (Ca, Zn, etc.), which confer them the qualities demanded by the service they have to provide
(resistance to oxidation, to shearing and to temperature, emulsifying and anti-foaming properties, low variability of
viscosity with temperature, etc.).
[0004] The discarded oils, after their use in motors and other machines, are called used oils. The regeneration of used
15 oils consists in recovering the lubricant bases by separating them from the additives as well as from their degradation
products (lighter petroleum fractions such as naphtha and gas-oil, and heavier ones such as asphalts and coke) and
the contaminants acquired in their use or collection, in garages and petrol stations, such as water, glycols and solvents.

BACKGROUND OF THE INVENTION

20
[0005] The separation of the additives, degradation products and contaminants of used oils is normally carried out by
distillation methods. In the patent WO 9407798 (Viscolube Italiana Sp, 1994) a typical distillation method is described
which uses high temperatures under vacuum distillation (around 350 °C) with the aim of breaking down the additives,
which also deteriorates the lubricant bases, which acquire colour and odour and contain oxygenated products. To obtain
25 quality lubricant bases by distillation at high temperature it is necessary to use final refining treatments with acid and
earths or by hydrogenation, which are onerous and complicated.
[0006] Also, the high temperatures employed cause fouling of the industrial equipment, which involves stopping the
process for cleaning.
[0007] As an alternative to the separation of the additives by distillation, the chemical demetallization has been de-
30 veloped by reacting the metal additives of the used oil with reagents that form metal salts. Thus, in the patent US 4247389
(Phillips Petroleum US, 1981) the used oil is treated with solutions of ammonium phosphate at temperatures of 320-420
°C. However, the demetallization treatment at these temperatures and the subsequent distillation of the demetallized
oil also produce odour and colour and yield unstable products, which require treating the bases obtained by hydrogenation
or by adsorbents, with the already indicated disadvantages of these final refining processes.
35 [0008] US3930988 discloses a process to reduce contaminants, ash content and content of metals, from used motor
oils, which comprises contacting said used oil with an aqueous solution of ammonium sulphate and/or ammonium
bisulphate under conditions to react with the metal compounds forming separable solids, and, optionally, further treating
the resulting motor oil under hydrogenation conditions.
[0009] On the other hand, there are some references to the use of alkaline hydroxides in the regeneration of used
40 oils. Thus, in patent DE 3433336 (BUSS AG, 1985) treatment with alkaline hydroxides is employed on the used oils
before proceeding to the separation of the additives and asphalts by distillation.
[0010] EP0690903 discloses a continuous process for the regeneration of used lubricant oils comprising the step of
preheating a lubricant oil to 140-160°C, adding an aqueous solution of sodium hydroxide, flash distillation to remove
water and low boiling hydrocarbon components, extraction and recovery of gas oil, and extraction of impurities by
45 fractional distillation under vacuum providing the separation of the base lubricant oil and a residue which concentrates
impurities.
[0011] Other methods use alkaline treatment of the lubricant fractions obtained after separating the additives and
asphalts by distillation (US 4834868, F. J. Lappin 1989, and WO 9826031, Sotulub, Tunisia 1997); or by extraction with
solvents and distillation (PCT/ES02/00354 Sener, Spain 2002), achieving in this way lubricant bases which do not require
50 final refining treatments by acid/earths or hydrogenation.
[0012] However, no antecedents have been about methods which use treatments with alkaline hydroxides before,
during or after chemical demetallization of used oils.
[0013] The present invention consists in a method of chemical demetallization followed by a distillation process of the
demetallized product in the presence of alkaline hydroxides, both carried out at moderate temperatures in such conditions
55 that lubricant bases are obtained with good characteristics of odour and colour, acidity and copper corrosion test and
complying with other typical specifications of lubricant bases of first refining.

2
 EP 1 712 608 B1

OBJECT OF THE INVENTION

[0014] The present invention has as its objective to regenerate used oils by means of a chemical demetallization
process which does not require costly treatments by hydrogenation or by acid and earths, to obtain lubricant bases
5 which comply which the specifications of virgin base oils.
[0015] The objective of the method is also to carry out the regeneration under moderate temperature conditions in a
way which will avoid fouling of the equipment and the need for frequent cleaning in installations for used oil treatment.
[0016] Likewise it is the objective of the method that the regeneration is carried out without producing emissions and
odours and without generating polluting solid wastes (acid residues, adsorbent earths, etc.).
10 [0017] Finally, it is also the objective of the present invention to carry out the regeneration of used oils by means of a
continuous industrial process which should require a low investment and have moderate operational costs, with high
returns, with the aim of making competitive installations of moderate capacity (15,000 - 30,000 t/y).

DETAILED DESCRIPTION OF THE INVENTION

15
[0018] The present invention provides a method for the regeneration of used mineral oils for obtaining lubricant bases
which comprises the following steps:

(a) demetallization of the used mineral oil by means of chemical treatment of said oil with an aqueous solution of a
20 chemical reagent which is an ammonium salt containing anions which form low solubility salts with the metals of
the oil, followed by the separation of the demetallized oil;
(b) distillation of the demetallized oil obtained in step (a) at atmospheric pressure and in the presence of alkaline
hydroxides; and
(c) distillation of the bottom liquid obtained in the atmospheric distillation of step (b) under vacuum and in the presence
25 of alkaline hydroxides to obtain lubricant bases.

[0019] Said method can be carried out in continuous mode or discontinuous mode, preferably in continuous mode.
[0020] The term "low solubility salts" in the context of the invention refers to salts which tend to precipitate in the
medium in which they are dissolved.
30 [0021] It has been verified experimentally that the elimination of the metals from the additives takes place with rea-
sonable demetallization yields (achieving a content in metals of about 100 ppm), when the oils are treated with ammonium
phosphates (mono or diammonium) at moderate temperatures (120-180 °C). This enables the operation to be carried
out without deterioration of the base oils, by avoiding the temperatures described in the literature (around 350 °C) for
achieving high demetallization yields (content in metals less than 10 ppm). Other ammonium salts, whose anions have
35 the property of forming insoluble or low solubility salts in water with metals present in used oils, are equally effective as
reagents in the demetallization. Thus, for example, besides the already mentioned mono- and diammonium phosphate,
triammonium phosphate, the mono- and diammonium sulphates, ammonium bisulphate and ammonium polyphosphates
or mixtures of these salts whose anions form insoluble or low solubility salts with the metals of the additives (mainly Ca,
Zn and Mg) or with other metals present in used oils (Pb, Fe, Cu and others) can be used.
40 [0022] So, in a particular embodiment of the method of the invention, the chemical reagent employed in step (a) is an
ammonium salt used in a proportion of 0.5% to 5% by weight of ammonium salt in relation to the used oil.
[0023] In another particular embodiment, said ammonium salt contains anions of the phosphate and sulphate groups,
and can be mono-ammonium or diammonium phosphate, or mono-ammonium or diammonium sulphate, or a mixture
thereof.
45 [0024] In a particular embodiment of the method of the invention, the chemical treatment of step (a) is carried out in
a continuous way in tubular reactors, or in one or several well-mixed reactors in series or in a combination of both
systems, and in which the reaction is carried out at temperatures between 120 °C and 180 °C, at pressures between 3
and 11 bar and with residence times between 10 and 120 minutes.
[0025] In another embodiment of the invention, the separation of step (a) is carried out continuously by means of an
50 adiabatic decompression which produces flash vaporisation, so that at least a part of the water and the light hydrocarbons
and solvents is vaporised. These light hydrocarbons and solvents are collected and decanted after their condensation.
[0026] The liquid obtained after the decompression and flash vaporisation is cooled and separated into a sludge which
containing the metal salts, an aqueous phase with excess of reagent and the demetallized oil. The separation of the
demetallized oil from the sludge of metal salts is carried out preferably by continuous centrifugation in one or two steps
55 in series.
[0027] Likewise, it has been verified that when the oils demetallized in this way are distilled at moderate temperatures
in the presence of alkaline hydroxides, lubricant bases of a quality equal to that of virgin bases of first refining is achieved,
avoiding the final treatments with acid and earths or by hydrogenation, which are necessary when using high temperatures

3
 EP 1 712 608 B1

in the demetallization and in the distillation.

[0028] Therefore, in another embodiment of the method of the invention, in step (b) the demetallized oil is distilled
continuously at atmospheric pressure in the presence of alkaline hydroxides, so that the remains of water, light hydro-
carbons and solvents are distilled, together with the ammonia released by the effect of the alkaline hydroxides.
5 [0029] In another particular embodiment, the distillate is subjected to condensation, followed by decanting, in such a
way that an organic phase is obtained which contains light hydrocarbons and solvents, and an aqueous phase which
contains ammonia. The non-condensables of the distillate are washed with water or with an aqueous solution of an acid
to retain the ammonia in aqueous solution, which is added to the aqueous ammonia phase obtained previously.
[0030] In order to carry out this atmospheric distillation in a simple way and to subject the product to the least possible
10 degradation, this operation of distillation at atmospheric pressure is carried out by indirect heating by means of a thermal
fluid at temperatures below 300 °C. Preferably, said atmospheric distillation is carried out in a continuous way subjecting
the demetallized oil to flash vaporisation at temperatures between 200 and 300 °C.
[0031] In another embodiment of the invention, in step (c) the bottom liquid obtained in the atmospheric distillation of
step (b) is distilled continuously under vacuum in a rectification column in the presence of alkaline hydroxides, preferably
15 at a pressure between 2 and 10 mbar at the top of the column and a column feed temperature between 310 and 335
°C, obtaining as side cuts a vacuum gas-oil, one or several fractions of lubricant bases and a bottom with characteristics
of fuel-oil or an asphalt component.
[0032] Likewise, in the method of the invention, for carrying out the vacuum distillation of step (c) under mild conditions
(temperatures lower than 330 °C), the fractionating column operates preferably at low pressure (2 to 10 mbar in the
20 head), with low pressure loss (packed column instead of valve or perforated plates) and by heating the feed to the column
by means of a thermal oil at a temperature less than 385 °C in a tubular heat exchanger, designed for high fluid velocity
in the tubes.
[0033] Similarly, the atmospheric distillation of step (b) is preferably performed in a tubular heat exchanger with high
fluid velocity through the tubes, a thermal oil preferably at a temperature less than 300 °C being the heating fluid which
25 circulates outside these tubes.
[0034] So, in a particular embodiment of the invention, the distillations of steps (b) and (c), that is, the distillation at
atmospheric pressure and the vacuum distillation, are carried out in tubular heat exchangers, in which the demetallized
oil obtained in step (a), or the bottom liquid obtained in the atmospheric distillation of step (b), circulates at high speed
inside the tubes and in which the heating fluid on the outside of these tubes is a thermal oil which circulates preferably
30 at temperatures lower than 300 °C in the atmospheric distillation and lower than 385 °C in the vacuum distillation.
[0035] Another characteristic of the method claimed is the use of proportions of alkaline hydroxides between 0.5%
and 5% by weight of oil, higher than that described in the literature (generally lower than 0.5% by weight), since sufficient
hydroxide is required to displace the ammonia in the demetallized oil.
[0036] Thus, in another particular embodiment of the method of the invention, the alkaline hydroxide used in steps
35 (b) and (c) is sodium hydroxide or potassium hydroxide or a mixture of both, which is added in a proportion of 0.5% to
5% by weight in relation to the demetallized oil, more preferably in a proportion of 0.5% to 3%, so that said addition is
carried out completely before the atmospheric distillation, or a part before the atmospheric distillation and a part before
the vacuum distillation.

40 DESCRIPTION OF THE FIGURES

[0037]

Figure 1 attached illustrates the method of the invention, carried out continuously, as is described below:
45
[0038] The current of used oil to be regenerated (1) and the chemical reagent (2), an aqueous solution of ammonium
phosphate, for example, are introduced into the reaction device (A) where they react to form metal salts.
[0039] As has been mentioned previously, the reaction device (A) could be a tubular reactor, one or several agitated
reactors in series, or a combination of both, where the reaction is preferably carried out at pressure and continuously.
50 [0040] The product which flows from the reaction device (A) is subjected to decompression in (B), some vapours being
separated which are condensed in (C) and decanted into two phases in (D), to give rise to an organic phase (3) of light
hydrocarbons and solvents (in the petrol and kerosene range) and an aqueous phase (4).
[0041] The liquid resulting from the decompression in (B) is cooled down in (E) and passes to the phase separation
system (F). Although the phase separation system (F) can be a combination of decanting, filtration and centrifugation
55 techniques, in the method of the present invention the separation of an oily sludge which contains the metal salts (6),
an aqueous phase with excess reagent (7), and the demetallized oil (5), are achieved advantageously by continuous
centrifugation in one or two centrifuges in series.
[0042] The aqueous solution which contains the excess reagent (7) can be recycled, at least partly, to prepare the

4
 EP 1 712 608 B1

chemical reagent again (1), while the liquid phase which contains the metal salts (6) is sent to a waste treatment plant
for its subsequent processing.
[0043] The demetallized oil (5), mixed with the alkaline hydroxide (8) is subjected to continuous atmospheric distillation
in (G), some vapours being obtained which are condensed in (H) and decanted in (I), obtaining in this way an organic
5 phase (9) of hydrocarbons and solvents, of a higher boiling point than those separated in the current (3), in the range
of kerosene and light gas-oil, and an aqueous phase (10) which contains the ammonia displaced by the alkaline reagent.
The non-condensables from the decanter (I) are washed with water or an aqueous solution of an acid to retain the
ammonia which is added to the aqueous ammonia solution (10) obtained previously.
[0044] The bottom of the atmospheric distillation, optionally with a second addition of alkaline hydroxide (8), is subjected
10 to rectification in a vacuum distillation column (J), thus separating a vacuum gas-oil (11), one or several side cuts of
lubricant bases (12) (SN-150 and SN-350, for example) and a column bottom (13) which has characteristics of fuel-oil
or of an asphalt component.

EXAMPLES
15
[0045] The examples which are shown below illustrate the method with their embodiment not necessarily constituting
the limits of the possibilities of the invention.
As used oil a product is employed with the following characteristics:

20 Colour: dark
Viscosity (ASTM D 445) at 100 °C: 13.3 cSt.
Water (ASTM D 95): 5% by weight
Metals: 3,500 ppm (Ca 1,750 ppm, Zn 854 ppm).
Distillation ASTM D 1160
25 I.P. = 228°C
F.P. = 520 °C
Distilled volume: 88%

Example No. 1 (Conventional demetallization and distillation treatment)

30
[0046] 1000 g of used oil is mixed with a saturated aqueous solution which contains 25 g of diammonium phosphate
and is heated for 60 minutes at 150 °C in an autoclave at 6 bar provided with mechanical agitation.
[0047] After the reaction, the autoclave is decompressed, condensing the vapours by means of a refrigerant and
collecting an aqueous condensate from which 20 g of light hydrocarbons and chlorinated products is separated by
35 decanting.
[0048] The contents of the autoclave, after decompression, is cooled down to ambient temperature and is centrifuged,
separating 30 g of a sludge containing metal phosphates (zinc, calcium, etc.), the aqueous phase containing the excess
ammonium phosphate and 910 g of demetallized oil containing 123 ppm of metals (Zn: 30 ppm; Ca: 39 ppm).
[0049] The 910 g of demetallized oil is distilled at atmospheric pressure until it reaches 280 °C. Thus 35 g of an organic
40 phase (light gas-oil, solvents, etc.) are obtained from which distilled water is decanted leaving a distillation bottom which
contains the demetallized oil.
[0050] Next, the bottom is vacuum distilled (15 mm Hg) obtaining 61 g of heavy gas-oil, 393 g of light base oil and
306 g of heavy base oil leaving in the distillation flask a bottom of 114 g of fuel-oil or an asphalt component.
[0051] The base oils obtained have a strong colour (2.5 to 5.0) and odour, an acidity greater than 0.1 mg KOH/g and
45 its IR spectrum showing a notable concentration of oxygenated products in the 1700 - 1730 cm-1 band, requiring an
additional treatment with adsorbent earths or by hydrogenation, to comply with the typical specifications of virgin lubricant
bases.
[0052] To verify this aspect, 250 cm3 of SN-350 oil obtained were taken (colour: 5.5, acidity: 0.14) and were treated
with 4% diatomaceous earths and 1% CaO for 20 minutes at 130 °C; after the reaction the mixture was cooled down
50 and filtered through a sintered glass disc.
[0053] The oil obtained had a colour of 2.5, an acidity of 0.04 and a light odour.
[0054] The recovery in lubricant fractions is 74% by weight of the starting used oil on a dry basis, before these additional
treatments with earths, and 72% after treatment with earths.
[0055] Example No. 1 shows that carrying out the distillation of the demetallized oil in low temperature conditions, an
55 oil base is obtained with good recoveries, but with characteristics which still require a final treatment with earths or by
hydrogenation.

5
 EP 1 712 608 B1

Example No. 2 (Treatment according to the claimed method)

[0056] 1000 g of used oil has is demetallized as shown in example 1.

[0057] The 910 g of demetallized oil is mixed with a saturated solution of potassium hydroxide containing 25 g of
5 potassium hydroxide and is distilled at atmospheric pressure until reaching 280 °C.
[0058] The distillate is collected over water to retain the ammonia released. Thus an ammonium solution is obtained
containing 15 g of ammonia, from which is decanted 33 g of an organic phase containing kerosene, light gas-oil and
solvents.
[0059] The bottom of the atmospheric distillation containing the sodium hydroxide added previously, is subjected to
10 rectification at vacuum (2 mm Hg) for obtaining 55 g of spindle oil (SN-80), 400 g of light base oil (SN-150) and 235 g
of heavy base oil (SN 350), leaving 200 g as a bottom. The recovery in lubricant bases is 67% in weight of used oil on
a dry basis.
[0060] The base oils obtained have characteristics typical of virgin base oils and comply with the normal specifications
of these products, without the need for further treatments, as shown below:
15
SN-150 SN-350 SN-80
Colour (ASTM D 1500) 0.5+ 1.5 0.5
Viscosity cSt at 40 °C (ASTM D445) 24 56 8.7
20
Acidity mg KOH/g (ASTM D664) 0.02 0.03 0.00
Water % (Karl Fisher) < 0.01 < 0.01 < 0.01
Flash point °C (ASTM D92) 236 243 ---
Ramsbottom Carbon % (ASTM D524) < 0.05 < 0.05 < 0.05

25
[0061] Example No. 2 demonstrates that demetallization followed by distillation, both carried out under moderate
temperature conditions and in the presence of an alkaline hydroxide, as specified in the present invention, produces
base oils with characteristics of base oils of first refining.

30
Claims

1. Method for the regeneration of used mineral oils for obtaining lubricant bases which comprises the following steps:

(a) demetallization of the used mineral oil by means of chemical treatment of said oil with an aqueous solution
35
of a chemical reagent which is an ammonium salt containing anions which form low solubility salts with the
metals of the oil, followed by the separation of the demetallized oil;
(b) distillation of the demetallized oil obtained in step (a) at atmospheric pressure and in the presence of alkaline
hydroxides; and
(c) distillation of the bottom liquid obtained in the atmospheric distillation of step (b) under vacuum and in the
40
presence of alkaline hydroxides to obtain lubricant bases.

2. Method according to claim 1, characterised in that the chemical reagent employed in (a) is an ammonium salt
used in a proportion of 0.5% to 5% by weight of ammonium salt in relation to the used oil.
45
3. Method according to claim 2, characterised in that the ammonium salt contains anions of the phosphate and
sulphate groups, and can be monoammonium or diammonium phosphate, or monoammonium or diammonium
sulphate, or a mixture thereof.

4. Method according to the previous claims, characterised in that in step

50

(a) the chemical treatment is carried out in a continuous way in tubular reactors, or in one or several well-mixed
reactors in series, or a combination of both systems; and where the reaction is carried out at temperatures
between 120 °C and 180 °C, at pressures between 3 bar and 11 bar and with residence times in the reactors
between 10 minutes and 120 minutes.
55

5. Method according to the previous claims, characterised in that in step (a) the separation is carried out continuously
by means of a flash vaporisation, so that at least a part of the water and the light hydrocarbons and solvents are

6
 EP 1 712 608 B1

vaporised, which are collected and decanted after their condensation, and a liquid is obtained, which after cooling
down, is separated into a sludge containing the metal salts, an aqueous phase with the excess reagent and the
demetallized oil.

5 6. Method according to claim 5, characterised in that the separation of the sludge containing the metal salts, the
aqueous phase with the excess reagent and the demetallized oil is carried out by continuous centrifugation in one
or two steps in series.

7. Method according to the previous claims, characterised in that in step (b) the demetallized oil is distilled continuously
10 at atmospheric pressure in the presence of alkaline hydroxides, so that the remains of water, light hydrocarbons
and solvents are distilled, along with the ammonia released by the effect of the alkaline hydroxides.

8. Method according to claim 7, characterised in that the distillate is subjected to condensation, followed by decanting,
in such a way that an organic phase is obtained which contains light hydrocarbons and solvents and an aqueous
15 phase which contains ammonia.

9. Method according to claim 8, characterised in that the non-condensables of the distillate are washed with water
or with an aqueous solution of an acid to keep the ammonia in aqueous solution, which is added to the aqueous
phase obtained in claim 8.
20
10. Method according to claims 7-9, characterised in that the atmospheric distillation is carried in a continuous way
by flash vaporisation at temperatures between 200 °C and 300 °C.

11. Method according to the previous claims, characterised in that in step (c) the bottom liquid obtained in the atmos-
25 pheric distillation of step (b) is vacuum distilled in a rectification column in a continuous way in the presence of
alkaline hydroxides, preferably at a pressure between 2 mbar and 10 mbar at the top of the column and a column
feed temperature between 310 °C and 335 °C, for obtaining a vacuum gas-oil or several fractions of lubricant bases
as side cuts and a bottom with characteristics of fuel-oil or an asphalt component.

30 12. Method according to the previous claims, characterised in that the distillations of steps (b) and (c) are carried out
in tubular heat exchangers, in which the demetallized oil obtained in step (a), or the bottom liquid obtained by
atmospheric distillation in step (b), circulates at high speed inside the tubes and in which the heating fluid on the
outside of these tubes is a thermal oil which circulates preferably at temperatures below 300 °C in the atmospheric
distillation and below 385 °C in the vacuum distillation.
35
13. Method according to the previous claims, characterised in that the alkaline hydroxide employed in steps (b) and
(c) is sodium hydroxide or potassium hydroxide, or a mixture of both, which is added preferably in a proportion of
0.5% to 5% in weight in relation to the demetallized oil, more preferably in a proportion of 0.5% to 3%, so that said
addition is carried out completely before the atmospheric distillation, or a part before the atmospheric distillation
40 and a part before the vacuum distillation.

Patentansprüche

45 1. Verfahren für die Regenerierung von Alt-Mineralölen zur Gewinnung von Schmiermittel-Basisflüssigkeiten, das die
folgenden Schritte umfasst:

(a) Demetallisierung des Alt-Mineralöls mittels chemischer Behandlung des Öls mit einer wässrigen Lösung
eines chemischen Reagens, bei dem es sich um ein Ammoniumsalz handelt, das Anionen enthält, die mit den
50 Metallen des Öls Salze mit geringer Löslichkeit bilden, gefolgt von der Abscheidung des demetallisierten Öls;
(b) Destillation des in Schritt (a) gewonnenen demetallisierten Öls bei atmosphärischem Druck und beim Vor-
handensein von Alkalihydroxiden; und
(c) Destillation der bei der atmosphärischen Destillation in Schritt (b) gewonnenen Bodenflüssigkeit im Vakuum
und beim Vorhandensein von Alkalihydroxiden, um Schmierstoff-Basisflüssigkeiten zu gewinnen.
55
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das in (a) verwendete chemische Reagens ein Am-
moniumsalz ist, das in einem Anteil von 0,5 bis 5 Gew.-% des Ammoniumsalzes im Verhältnis zu dem Altöl eingesetzt
wird.

7
 EP 1 712 608 B1

3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das Ammoniumsalz Anionen der Phosphat- und
Sulphatgruppe enthält und Monoammonium- oder Diammoniumphosphat oder Monoammonium- oder Diammoni-
umsulphat oder ein Gemisch daraus sein kann.

5 4. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass in Schritt (a) die chemische
Behandlung kontinuierlich in röhrenförmigen Reaktoren oder in einem oder mehreren Rührreaktor/en in Reihe oder
einer Kombination aus beiden Systemen ausgeführt wird, und wobei die Reaktion bei Temperaturen zwischen 120
°C und 180 °C, bei Drücken zwischen 3 bar und 11 bar und bei Verweilzeiten in den Reaktoren zwischen 10 Minuten
und 120 Minuten ausgeführt wird.
10
5. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass in Schritt (a) die Abscheidung
kontinuierlich mittels Stoßverdampfung so ausgeführt wird, dass wenigstens ein Teil des Wassers und der leichten
Kohlenwasserstoffe und Lösungsmittel verdampft werden, die nach ihrer Kondensation aufgefangen und dekantiert
werden, und eine Flüssigkeit gewonnen wird, die nach Abkühlung in einen Schlamm, der die Metallsalze enthält,
15 eine wässrige Phase mit dem überschüssigen Reagens und das demetallisierte Öl getrennt wird.

6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Trennung des Schlamms, der die Metallsalz
enthält, der wässrigen Phase mit dem überschüssigen Reagens und des demetallisierten Öls durch kontinuierliches
Zentrifugieren in einem oder zwei Schritt/en in Reihe ausgeführt wird.
20
7. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass in Schritt (b) das demetallisierte
Öl kontinuierlich bei atmosphärischem Druck beim Vorhandensein von Alkalihydroxiden so destilliert wird, dass die
Reste von Wasser, leichten Kohlenwasserstoffen und Lösungsmitteln zusammen mit dem Ammonium destilliert
werden, das durch die Wirkung der Alkalihydroxide freigesetzt wird.
25
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Destillat Kondensation, gefolgt von Dekantieren,
so unterzogen wird, dass eine organische Phase gewonnen wird, die leichte Kohlenwasserstoffe und Lösungsmittel
sowie eine wässrige Phase enthält, die Ammonium enthält.

30 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die nicht kondensierbaren Bestandteile des Destillats
mit Wasser oder mit einer wässrigen Lösung einer Säure gespült werden, um das Ammonium in wässriger Lösung
zu halten, die zu der in Anspruch 8 gewonnenen wässrigen Phase hinzugefügt wird.

10. Verfahren nach den Ansprüchen 7-9, dadurch gekennzeichnet, dass die atmosphärische Destillation kontinuierlich
35 mittels Stoßverdampfung bei Temperaturen zwischen 200 °C und 300 °C ausgeführt wird.

11. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass in Schritt (c) die Bodenflüssig-
keit, die bei der atmosphärischen Destillation von Schritt (b) gewonnen wird, im Vakuum in einer Rektifiziersäule
kontinuierlich beim Vorhandensein von Alkalihydroxiden, vorzugsweise bei einem Druck zwischen 2 mbar und 10
40 mbar an der Oberseite der Säule und einer Säulen-Beschickungstemperatur zwischen 310 °C und 335 °C destilliert
wird, um ein Vakuum-Gasöl oder mehrere Fraktionen von Schmiermittel-Basisflüssigkeiten als Seitenprodukte und
eine Bodenfraktion mit Eigenschaften von Gasöl oder einer Asphaltkomponente zu gewinnen.

12. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass die Destillationsvorgänge in
45 Schritt (b) und (c) in röhrenförmigen Wärmetauschern ausgeführt werden, in denen das in Schritt (a) gewonnene
demetalliserte Öl oder die durch atmosphärische Destillation in Schritt (b) gewonnene Bodenflüssigkeit mit hoher
Geschwindigkeit im Inneren der Röhren zirkuliert, und wobei das Heizfluid an der Außenseite dieser Röhren ein
Thermalöl ist, das vorzugsweise bei Temperaturen unter 300 °C bei der atmosphärischen Destillation und unter
385 °C bei der VakuumDestillation zirkuliert.
50
13. Verfahren nach den vorangehenden Ansprüchen, dadurch gekennzeichnet, dass das in den Schritten (b) und
(c) eingesetzte Alkalihydroxid Natriumhydroxid oder Kaliumhydroxid oder ein Gemisch aus beiden ist, das vorzugs-
weise in einem Anteil von 0,5 bis 5 Gew.-% im Verhältnis zu dem demetallisierten Öl, vorzugsweise in einem Anteil
von 0,5 bis 3 %, so zugesetzt wird, dass der Zusatz vollständig vor der atmosphärischen Destillation ausgeführt
55 wird oder ein Teil vor der atmosphärischen Destillation und ein Teil vor der Vakuumdestillation.

8
 EP 1 712 608 B1

Revendications

1. Procédé pour la régénération d’huiles minérales usagées pour obtenir des bases de lubrifiant qui comprend les
étapes suivantes :
5
(a) démétallisation de l’huile minérale usagée au moyen d’un traitement chimique de ladite huile avec une
solution aqueuse d’un réactif chimique qui est un sel d’ammonium contenant des anions qui forment des sels
de faible solubilité avec les métaux de l’huile, suivie par la séparation de l’huile démétallisée ;
(b) distillation de l’huile démétallisée obtenue dans l’étape (a) à pression atmosphérique et en présence d’hy-
10 droxydes alcalins ; et
(c) distillation du liquide de fond obtenu dans la distillation atmosphérique de l’étape (b) sous vide et en présence
d’hydroxydes alcalins pour obtenir des bases de lubrifiant.

2. Procédé selon la revendication 1, caractérisé en ce que le réactif chimique utilisé dans (a) est un sel d’ammonium
15 utilisé dans une proportion de 0,5 % à 5 % en poids de sel d’ammonium par rapport à l’huile usagée.

3. Procédé selon la revendication 2, caractérisé en ce que le sel d’ammonium contient des anions des groupes
phosphate et sulfate, et peut être un phosphate de monoammonium ou de diammonium ou un sulfate de monoam-
monium ou de diammonium, ou un mélange de ceux-ci.
20
4. Procédé selon les revendications précédentes, caractérisé en ce que dans l’étape (a) le traitement chimique est
conduit de manière continue dans des réacteurs tubulaires, ou dans un ou plusieurs réacteurs correctement mé-
langés en série, ou une combinaison des deux systèmes ; et où la réaction est conduite à des température comprises
entre 120 °C et 180 °C, à des pressions comprises entre 3 bars et 11 bars et avec des temps de séjour dans les
25 réacteurs compris entre 10 minutes et 120 minutes.

5. Procédé selon les revendications précédentes, caractérisé en ce que dans l’étape (a) la séparation est conduite
en continu au moyen d’une vaporisation flash, de sorte qu’au moins une partie de l’eau et des hydrocarbures légers
et des solvants sont vaporisés, qui sont collectés et décantés après leur condensation, et un liquide est obtenu, qui
30 après refroidissement, est séparé en une boue contenant les sels de métaux, une phase aqueuse avec le réactif
en excès et l’huile démétallisée.

6. Procédé selon la revendication 5, caractérisé en ce que la séparation de la boue contenant les sels de métaux,
la phase aqueuse avec le réactif en excès et l’huile démétallisée est conduite par centrifugation continue en une
35 ou deux étapes en série.

7. Procédé selon les revendications précédentes, caractérisé en ce que dans l’étape (b) l’huile démétallisée est
distillée en continu à pression atmosphérique en présence d’hydroxydes alcalins, de sorte que les résidus d’eau,
d’hydrocarbures légers et de solvants soient distillés, avec l’ammoniac libéré par l’effet des hydroxydes alcalins.
40
8. Procédé selon la revendication 7, caractérisé en ce que le distillat est soumis à condensation, suivi par une
décantation, de telle manière qu’une phase organique soit obtenue qui contient des hydrocarbures légers et des
solvants et une phase aqueuse qui contient de l’ammoniaque.

45 9. Procédé selon la revendication 8, caractérisé en ce que les non condensables du distillat sont lavés avec de l’eau
ou avec une solution aqueuse d’un acide pour maintenir l’ammoniaque en solution aqueuse, qui est ajoutée à la
phase aqueuse obtenue dans la revendication 8.

10. Procédé selon les revendications 7 à 9, caractérisé en ce que la distillation atmosphérique est conduite d’une
50 manière continue par vaporisation flash à des températures comprises entre 200 °C et 300 °C.

11. Procédé selon les revendications précédentes, caractérisé en ce que dans l’étape (c) le liquide de fond obtenu
dans la distillation atmosphérique de l’étape (b) est distillé sous vide dans une colonne de rectification d’une manière
continue en présence d’hydroxydes alcalins, de préférence à une pression comprise entre 2 mbar et 10 mbar au
55 sommet de la colonne et une température d’alimentation de colonne comprise entre 310 °C et 335 °C, pour obtenir
un gazole sous vide ou plusieurs fractions de bases de lubrifiant en tant que fractions latérales et un fond avec des
caractéristiques de mazout ou un composant d’asphalte.

9
 EP 1 712 608 B1

12. Procédé selon les revendications précédentes, caractérisé en ce que les distillations des étapes (b) et (c) sont
conduites dans des échangeurs de chaleur tubulaires, dans lesquels l’huile démétallisée obtenue dans l’étape (a),
ou le liquide de fond obtenu par distillation atmosphérique dans l’étape (b), circule à vitesse élevée à l’intérieur des
tubes et dans lesquels le fluide chauffant à l’extérieur de ces tubes est une huile thermique qui circule de préférence
5 à des températures au-dessous de 300 °C dans la distillation atmosphérique et au-dessous de 385 °C dans la
distillation sous vide.

13. Procédé selon les revendications précédentes, caractérisé en ce que l’hydroxyde alcalin utilisé dans les étapes
(b) et (c) est l’hydroxyde de sodium ou l’hydroxyde de potassium, ou un mélange de ceux-ci, qui est ajouté de
10 préférence dans une proportion de 0,5 % à 5 % en poids par rapport à l’huile démétallisée, plus préférablement
dans une proportion de 0,5 % à 3 %, de sorte que ledit ajout soit effectué totalement avant la distillation atmosphérique,
ou une partie avant la distillation atmosphérique et une partie avant la distillation sous vide.

15

20

25

30

35

40

45

50

55

10
EP 1 712 608 B1

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 EP 1 712 608 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• WO 9407798 A [0005] • EP 0690903 A [0010]

• US 4247389 A [0007] • US 4834868 A, F. J. Lappin [0011]
• US 3930988 A [0008] • US 1989 A [0011]
• DE 3433336, BUSS AG [0009] • WO 9826031 A [0011]
• DE 1985 [0009] • ES 0200354 W [0011]

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