Note: Descriptions are shown in the official language in which they were submitted.
1094S39
- 2 -
The present invention relates to a process for
the preparation of lubricating oils with a viscosity
index (VI) lower than 90, namely oils with a low vis-
cosity index (LVI oils, VI < 30) and oils with a
medium viscosity index (MVI oils, VI varying between
30 and 90). (The viscosity indices mentioned in this
specification relate to values determined by ASTM
method D 2270-64). Such oils may be used in all cases
in which the VI is not of vital importance, for instance
in the industry.
For the preparation of HVI oils (high VI, i~e.
VI of at least 90) waxy crude oils are used as the
feed, since it is impossible to prepare from naphthenic
crude oils lubricating oils with the desired viscosity
index by conventional processes, such as distillation, -
deasphalting, extraction and dewaxing.
MVI and LVI oils are normally prepared from
naphthenic crude mineral oils by application of
the following processing stages: distillation, ex-
tractior (only for MVI oils) and, if desire~, a terminaltreatment, for instance an acid or hydrogen treatment.
The term "waxy crude oils" relates to crude
mineral oils containing a considerable quantity of
paraffins having a melting point above 15C. Distillate
and residual fractions of waxy crude oils containing
such paraffins indeed have a relatively high pour
109 ~539
point and re~oval of the paraffins is necessary for
the preparation of fuel and lubricating oils that
can be used at ambient or at a lower temperature.
The ter~"naphthenic crude oils" relates to
crude mineral oils containing no or hardly any
paraffins with a melting point above 15C. Indeed,
fuel oils and lubricating oils prepared from
naphthenic crude oils need not be dewaxed.
MVI and LVI oils are generally prepared by blending
vacuum distillate fractions prepared from a naphthenic
crude oil; these fractions are denoted by a number
that is equal to their viscosity in seconds Redwood
at l40F. Examples of fractions are LVI 50, LVI 140,
LVI 450, LVI 700 and LVI llO0. If,an ~I oil has to
be prepared from one or more of these fractions, the
VI should be increased somewhat. This can be achieved
by partly removing by extraction the aromatic compounds
of one or more of the fractions to be included in
the MVI oil.
Since the availability of naphthenic crude oils
may become a problem, it would be attractive il the
distillate fractions for the preparation of LVI and
MVI lubricating oils obtained from naphthenic crude
oils could be replaced by other components. Naturally,
such a replacement should not unduly affect the
properties of the lubricating oil, such as colour
and colour stability.
10~,~539
-- 1l
In areas only having facilities for HVI lubrlcating
oil manufacture, it would be particularly advantageous
if MVI and~or LVI lubricating oils could be prepared
from the HVI feed, since the transport of fractions
from a naphthenic crude oil from the place of production
to the ar~ concerned may be a difficult and costly affair.
It would be especially advantageous if MVI and I,VI
lubricating oils could be prepared from a waxy
crude oil without an appreclable drop in the yield
of HVI lubricating oil prepared from this feed.
The criterion to be met by such an MVI and/or LVI
lubricating oil to be prepared from an HVI lubricating
oil feed is that the viscometric and colour properties
shoul~ be comparable with those of MVI and/or LVI
lubricating oils prepared entirely from a naphthenic
crude mineral oil as the feed.
It has now been found that LVI and ~VI lubricating
oils that are based entirely on waxy starting materials
can be prepared by blending two or more components
obtained as by-products in the preparation of HVI
lubricating base oils.
Normally, the preparation of HVI lubricating base
oils is carried out as follows. A waxy crude mineral
oil is separated by d;stillation at atmospheric
pressure into a number of distillate fractions (vi~.
in succession, one or more gasoline, kerosine and
lO9 ~S3
light gas oil fractions) and a residue (called the
long residue). By distillation at reduced pressure
this long residue is subsequently separated into
a number of distillate fractions (viz. in succession,
one or more heavy gas oil, spindle oil, light machine
oil and medium machine oil fractions) and a residue
(called the short residue), From the lubricating
oil fractions obtained in the distillation at reduced
pressure the corresponding lub-icating oils are
prepared by refining. ~efining of the spindle oil,
light machihe oil and medium machine oil fractions
takes place by removal of at least part of the aromatics
and paraffins from these fractions, In the refining
of the short residue first of all asphalt is removed
from the residue.
From the deasphalted oil thus obtained at least
part of the aromatics and paraffins is subseauently
removed, The residual lubricating oil thus prepared
is referred to as bright stock. The processes for the
removal of asphalt~ aromatics and paraffins are called
hereinafter: deasphalting, aromatics extraction and
dewaxing.
In the preparation of a lubricating base oil
from a residual lubricating oil fraction deasphalting
is carried out because the presence of asphalt in
lubricating oils is undesirable and because it also
interferes with subsequent refining treatments.
1094539
-- 6 --
The aim of the aromatics extraction is to increase
the viscosity index and to improve the colour as well
as the oxidation and colour stability of the fractions.
The aroma~ic extracts are by-products of the HVI
lubricating oil preparation and they have little
value. They are generally used as fuel components.
Dewaxingreduces the pour point of the lubricating
oil fractions, thus making them suitable for use at
temperatures lower than ambient temperature.
The aromatic extracts described hereinbefore,
which generally have a relatively low VI, are, as far
as their viscosity properties are concerned, suitable
for use as components for MVI and LVI oils. However3
the aromatic extracts generally have an unattractive
colour as well as a poor colour stability. Conse~uently,
they are not used as lubricating oil components in
cases where a light colour and/or a good colour stability
are desirable.
It has been found that the colour as well as thé
colour stability of aromatic extracts from both distillate
and deasphalted residual lubricating oil fractions de-
rived from waxy crude mineral oils can be considerably
improved by subjecting these extracts to a catalytic
hydrogen treatment. It has further been found that
after this catalytic hydrogen treatment the aromatic
extracts are eminently suitable for use as blending
10~94539
components for the preparation of LVI and ~NI oils based completely on waxy
starting materials. Apart from the above-mentioned hydrogen-treated aromatic
extracts dewaxed gas oils can also be included in the blends, provided that
these gas oils have a 5% boiling point of at ieast 275C and have been obtained
in the distillation of waxy crude mineral oils. For example, in the pre-
paration of the LVI and MNI oils one or more dewaxed gas oils may be blended
with either one or more hydrogen-treated aromatic extracts of distillate
lubricating oil fractions, or with one or more hydrogen-treated aromatic
extracts of residual lubricating oil fractions, or with a blend of one or
10 more hydrogen-treated aromatic extracts from each of the aforementioned
categories.
Generally, the present invention provides a process for the pre-
paration of a lubricating oil with a viscosity index lower than 90, said
lubricating oil comprising a blend of two or more comRonents prepared from
crude mineral oils, said components being selected from the class of groups
consisting of group A, group B and group C, said process comprising blending
one or re components selected from group C with one or more components
selected from group A and/or with one or re components selected from group
B,
gro~p A being aromatic extracts from
deasphalted residual lubricating oil fractions,
group B being aromatic extracts from distillate lubricating
oil ~ractions
group C being gas oils from distillate lubricating oil fractions,
wherein said deasphalted residual lubricating oil fractions and said distil-
late lubricating oil fractions are prepared from waxy crude mineral oils,
wherein said gas oils have a 5% boiling point of at least 275C and wherein
a) prior to said blending, at least one of said components is
subjected to a catalytic hydrogen treatment, a dewaxing treatment or both
and/or
~ -7-
1(~94S39
b) after said blending~ the obtained blend is subjected to a
catalytic hydrogen treatment, a dewaxing treatment or both, provided that
1) each of the one or more components sel~cted from group A or
group B is at least subjected to a catalytic hydrogen treatment either before
or after said blending and
2) each of the one or more components selected from group C is
at least subjected to a dewaxing treatment either before or after said
blending.
According to the present invention each of the one or more com-
ponents selected from group A or group B may be subjected to a catalytic
hydrogen treatment before blending.
According to the present invention each of the one or more com-
ponents selected from group C may be subjected to a dewaxing treatment
before blending. Preferably the pOUT point of each of the one or more
components selected from group C is reduced by dewaxing to -10C or lower.
According to the present invention each of the one or more com-
ponents of group C may be subjected to a catalytic hydrogen treatment before
blending.
The present invention provides in particular a process for the
preparation of a lubricating oil with a viscosity index lower than 90, said
lubricating oil comprising a blend of two or more components prepared fiom
crude mineral oils, said components being selected from the class of groups
consisting of group A, group B and group C, said process comprising blending
one or more components selected from group C with one or more components
selected from group A and/or with one or more components selected from
group B,
group A being aromatic extracts from deasphalted residual
lubricating oil fractions,
group B being aromatic extrac~s from distillate lubricating oil
3Q fractions
~,'
lO~'~S~'39
group C being gas oils from distillate lubri~ating oil fractions,
wherein said deasphalted residual lubricating oil fractions and said distil-
late lubricating oil fractions are prepared from waxy crude maneral oils,
wherein said gas oils have a 5% boiling point of at least 275C and provided
that, prior to said blending,
a) each of the one or more components selected from group A or
group B is either subjected to a catalytic hydrogen treatment or to a
dewaxing treatment and a catalytic hydrogen treatment, and
b) each of the one or more components selected from group C is
either subjected to a dewaxing treatment or to a catalytic hydrogen treatment
and a dewaxing treatment.
In the process according to the invention at least one of the
~lending components should be prepared from an aromatic extract from distil-
late lubricating oil fraction or from a deasphalted residual lubricating oil
fraction. Suitable extractants include furfural, phenol and sulphur dioxide.
It is preferred to use furfural for this purpose. Extraction, when applied
to a residual lubricating oil fraction, should be preceded by asphalt removal.
Deasphalting can very suitably be carried out by contacting the residual
lubricating oil fraction at elevated temperature and pressure with an excess
of a lower hydrocarbon such as propane, butane, pentane or a mixture thereof.
It is preferred to use propane for this purpose.
In the preparation of lubricating oils according
-8a-
, ,,
109~S39
g
to the invention at least one of the blending components
should be an aromatic extract, which e~tract has been
subjected to a catalytic hydrogen treatment. In
this specification "a catalytic hydrogen treatment"
should be taken to mean a treatment in which the oil con-
cernedis contacted at elevated temperature and pressure
and in the presence of hydrogen with a c~talyst
comprsing one or more metals having hydrogenation
activity. Preference is given to catalysts comprising
nickel and/or cobalt and, in addition, molybdenum and/cr
tungsten on a carrier. Very suitable metal combinations
are nickel-molybdenum, cobalt-molybdenum and nickel-
tungsten Preferably, alumina is used as the carrier.
The metals may be present in the catalysts in the
metallic form or in the form of their oxides or sulphides.
Preference is given to the use of catalysts in the
sulphidic form. In addition to one or more metals
having hydrogenation activity, the catalysts may
contain promoters such as fluorne, boron and/or phosphorus.
The conditions under which the catalytic hydrogen treat-
ment of the aromatic extracts can be carried out may
vary widely. The catalytic hydrogen treatment is
preferably carried out at a temperature of 250-425C
and in particular of 300-400C,a hydrogen partial
pressure of 50-200 bar and in particular of 75-175 bar,
a space velocity of 0.5-5 kg.l 1.h 1 and in particular
109~539
- 10 -
of 0.5-2 5 kg.l 1.h 1and a hydrogen/oil ratio of
250-25()0 Nl.kg 1 and in particular of 500-2000
Nl.kg 1 (N= normal temperature and pressure)..Further,
it is preferred for the catalytic hydrogen treatment
of the aromatic extracts to be carried out such
that after removal of volatile components from the
hydrogen-treated product an oil is obtained with a
colour according to AS~M-D 1500 of 5 or lighter and
in particular of 3~5 or lighter, whose colour rating
after 24 hours at 100C has increased by not more than
3 units and ln particular by not more than 1.5 units.
If it is intended in the process according to
the inventi~ to use two or more aromatic extracts, these
aromatic extracts can be subjected to a catalytic
hydrogen treatment.before or after mixing.
Suitable gas oils can be obtained in the dis-
stillation of waxy crude oil under atmospherlc pressure
as well as gas oils obtained in the vacuum d~tillation
of waxy crude oils. Preference is given to gas oils
whose pour point has been reduced by dewaxing to
-10C or lower and in particular to -15C or lower.
For dewaxing of the gas oils all the methods known
in the art are in principle suitable, for instance
cooling down in the presence of a mixture of methyl
ethyl ketone and toluene. Gas oils being obtained
on a large scale as by-products in the peparation
~09i~539
of wax by dewaxing of gas o;ls with the aid of urea,
preference is given to gas oils dewaxed in this way
as blending components ~or the present lubricating
oils. If desired, the gas oils, before being used
as blending components, may be subjected to a catalytic
hydrogen treatment to improve their colour and colour
stability. This catalytic hydrogen treatment may be
carried out either before or after dewaxing. Since
the gas oils will often originate from a process for
the preparation of wax, the catalytic hydrogen treatment
will preferably be carried out after dewaxing. The
catalysts and conditions that are preferably used in
the catalytic hydrogen treatment of gas oils are the
same as those ~entioned hereinbefore ~or the aromatic
extracts. It may be observed that in the catalytic
hydrogen treatment of gas oils special preference is giver
to temperatures between 300 and 350C, whereas in the
catalyt;ic hydrogen treatment of aromatic extracts of
distillate lubricating oil fractions and aromatic
extracts from deasphalted residual lubrcating oil
fractions special preference is given to temperatures
between 350 and 375C and between 375 and 400CC,
respectively.
If it is intended to use a gas oil thathas been
subjected to a catalytic hydrogen treatment, it may
.39
be preferable first to blend it with the aromatic extracts to be incorporated
in the lubricating oil and to subject the blend to a catalytic hydrogen
treatment.
In the preparation of lubricating oil according to the invention
a gas oil blending component will generally have been dewaxed before it is
blended with the other components. If desired, dewaxing of the gas oil may
be carried out after it has been blended with the other components. This
embodiment may be preferred, for instance, ~Yhen in the preparation of lub-
ricating oil use is made of aromatic extracts having such a high pour point
that they must be dewaxed in view of the pour point of the lubricating oil
to be prepared. This dewaxing may take place before or after blending with
the other components, but if a gas oil is used as the blending component,
preference is given to blending the gas oil and the a~omatic extracts having
æ high pour point without first dewaxing the components~ and dewaxing is
applied to the blend.
As explained hereinbefore the pour point of the lubricating oils
prepared according to the invention may be reduced by dewaxing the blending
components used and/o~ dewaxing the blend. A reduction of the pour point of
the lubricating oils may also be effected
-12-
'; `
, ~
109~5:~9
- ~3 --
by addition of a pour point reducer. Examples of
suitabe pour point reducers are condensation products
of chlorinated paraffins with chlorinated naphthalene
or with phenol and copolymers of ethene and vinyl
acetate. Preference is given to polymers with unbranched
aliphatic hydrocarbon side chains with at least 16
carbon atoms, such as polymers of alkyl esters of
unsaturated monocarboxylic acids, in particular of
acrylic acid and methacrylic acid, in which the alkyl
chains are unbranched and contain 16-22 car~onatoms
and copolymers of these alkyl esters with other
monomers such as vinylpyridines. The amount of pour
point reducer that may be added to the LVI and ~VI
lubricating oils prepared according to the inventlon
may vary within wide limits dependent on the pour-point
-redùcing effect of the additive concerned and the
pour point reduction that is aimed at. In general
the amount of pour point reducer applied is 0.01
to 1 %w.
The amounts of the different blending components
that can be used in the process according to the
invention, may vary within wide limits dependent on
the desired viscosity of the lubricating oil to
be prepared. For the preparatio of lubricating oils
with a viscosity Redwood I at 140F below 200 s,
it is preferred to blend 50-98 parts by weight
~0'~5;~'~
of one or more components selected from group B with 2~50 parts by weight of
one or re components selected from group C.
In addition to the pour point reducers mentioned hereinbefore,
also other quality-improving additives may be incorporated in the lubricating
oils prepared according to the invention. Examples of such additives are
antioxidants (e.g. alkyl phenols), detergent additives ~e.g. calcium petroleum
sulphonates, calcium alkylsalicylates and polyamines containing a hydrocarbon
chain of at least S0 carbon atoms such as polyisobutenyltetraethylene-
pentamine) and high pressure additives such as zincdialkyldithiophosphates.
Lubricating oils prepared according to the invention have a good colour and
colour stability. These properties can be further improved by subjecting
the lubricating oils to an activated eaTth treatment.
The lubricating oils prepared according to the invention may b~
used for various applications, for instance for automotive engines, gear
oils, axle oils, mould oils in concrete and foundry technology, in lub~icating
greases and printing inks and in the processing of rubbers and fibres.
-14-
,,'
i539
- 15 --
The invention will now be illustrated with the
aid of the following example.
EXAMPLE
From each of two waxy crude oils from the Middle
East (Crude oils 1 and 2) a heavy gas oil fraction,
three distillate lubicating oil fractions (a spindle
oil, a light machine oil and a medium machine oil
fraction, respectively) and a residual lubricating oil
fraction were isolated by atmospheric distillation followed
by vacuum distillation. The heavy gas oil fractions were
dewaxed with urea, the distillate lubricating oil
fractions were extacted with furfural and the residual
lubricating oil fractions were deasphalted with propane
and subsequently extracted with furfural. Thus, from
each of the crude oils the following ~ls were prepared:
a dewaxed gas oil (DGO), an aromatic extract of a
spindle oil (ESO), an aromatic extractof a light machine
oil (ELMO), an aromat1c extract of a medium machine oil
(EMMO) and an aromatic extract of a residual lubricating
oil (ERO). With the exception of the aromatic extract
of the rsidual lubricating oil prepared form crude
oil 1, each of the above-mentioned oilæ (Oils 3-11)
was used in the preparation of lubricating oils
according to the invention. Some properties of oils
3-11 are collected in Table A.
10~'~53~
~j C~l
l l
~1l j~ C~l CO + O~ I I
1 1
o CO o
~ ~ CO +
CO¦U~ N r I
1~ ~ N ~ u~
:~ ~ C~ I (
0 1 1
~01 ~ ~ Co
O 0 11
1 + L~
o Ir~ o~ o o
U~
l l
1 1
1 1
O ~) ~) O I I
O O ~ 1 1
~1 0 ~ I I
0 ~ ~ ~ I I
~ O ~ H O l l
ii i
-- lo --
'V'
A
109 ~539
With the exception of oil 3, all the other oils
mentioned in Table A were subjected to a eatalytic hydrogen
treatment using two eatalysts (Catalysts 1 and 2) with the
following composition:
Cat. 1 = Ni/Mo/P/Al2O3 eatalyst containing 3.8 pbw nickel, 16.0
pbw molybdenum and 4.0 pbw phosphorus per 100 pbw
alumina carrier.
Cat. 2 = Ni/W/F/Al2O3 catalyst containing 30.6 pbw nickel,
59.2 pbw tungsten and 10.1 pbw fluorine per 100 pbw
alumina earrier.
The products obtained in the catalytic hydrogen treatment
were topped to remove the lower boiling constituents. In this
process topping temperatures were applied varying between 270
and 330C. The conditions that were applied in the catalytic
hydrogen treatment as well as some properties of the oils
obtained after hydrogen treatment and topping (Oils 12-24) are
colleeted in Table B.
~O~ S39
N ¦ ~1 I C`J r -
~1l ~ "~ Oo O
t o
~1 1 i ~ ~ o t
21 1 ~ ~ ,,
o o t--
I ~ ~ o
~o I ,~, g t_
,, o
o o o
,. .
m
~i ~01 ~1 C~l U~ O
t-l ~ O g O
~1 ~ol , ~ L~ oO t .
I ~ ~ o
g ~_
1 ~ ~ O
I
o g t_
~ i-l
o~ ~ C)
i oV ^
o
o l ~ q I o ~ ~ ~ h ~ bD
-- 18 --
r,~ y.
iO~ t53~
~1 ~u~ ~ ~ 1 1
~o ~ ~ ~ + 1 1
1,1
~ 1
~1 oL~ U~
O + 1 1
f l
1 1
c~l U\ o o ~ I' I
C\J ¦ ~ O N
1 1
1' 1
~I co O . o ~ ~, I
~D ~ ~ ~ + 1. 1
I I
1 1
C"ll g g IA 11~ C I I
+ 1 1
~1 1, 1
o~ll O O ~ IA
~ O ~ N + l l
COl g o O 1` I
fY) + l I
1 1
~O C~l O O
-11 g oLr~
O I ~O C~J O O I l I
_, ~1 1~ 1 I
11
CO" U
E-l 1~ ~:1 1 I
1 1
~1 ou\ LJ'~ ~ I I
~O ~ ~ 1~ + I I
1 1
~11 o11
oO O
01 ~~ J00 1 1
rl O ~ a) o ~ o ~ I I
O ~ ~ ~ 0
O ~ O Oq~~ O O
-- 1, --
~. ~
109.~53~
- 20 -
Fin~lly, 15 lubricating oils according to the
invention (Lubricating oils I-XV) were prepared by
blending two or three oils selected from oils 3, 7
and 12-24. In addition, a lubricating oil according
to the invention (Lubricating oil XVI) was prepared
by blending oils 7 and 8 follo~Jed by a catalytic
hydrogen treatment of the blend and topping of the
hydrogen-treated product at 270C. The h~Tdrogen treat~
ment of the blend was carried out using cat. 2 at a
temperature of 325C, a hydrogen partial pressure of
150 bar, a space velocity of 0.7 kg.l 1.h 1 and a
H2/oil ratio of 600 Nl.kg 1. By a treatment of
lubricating oil XIV with 3 %w of activated earth
an improvement was effected in the colour a and
in the colour after 24 h at 100C, from L 3.0 to
~L 2.5 and from L 6.o to L 3.5, respectively.
The compositions of lubricating oils I-XVI
as well as some properties of these lubricating oils
are collected in Table C. The type of blend of the
lubricating oils concerned is also indicated in
the table on the basis o~ the blending components
used in the preparation and selected from groups
A, B and C, viz.
1. One or more components selected from group C
with one or more components selected rom
group A (type CA),
10~'1539
- 21 -
2. One or more components selected ~rom group C
with one or more components ~rom group B
(type CB),
3. one or more component,s selected from group C
with one or more components selected ~rom
group A and with one or more components
selected from group B (type CAB), and
4. two or more components selected ~rom group B,
with each other (ty,pe BB).
All the lubricating oils prepared according
to the invention had a VI lower than 90.
lO~ t5;3~
H¦ t-- O CO O
~1 o u~
Xl ~ ~ ~ co
H I ~ O ~t 1
H N
Xl
I
H ¦ ~ O ~ C~l H CO
~H I ~ O CU O
~ ~ C~ ~O
H I H ~ ~1 11
H I ~0 CO CO C`J
~)
gl ~ O
H, I U~ O o
~1 ~ o ~ o
CO ~I N
H I ~ O O
H I ~ O C~ l ~ CO
H¦ u~ H ~ H
I
H l ~ O ~ O
I
H¦ U~ O ~ O
~1 C~ C\l CO
æ~ o
l a~ g æ ~ ~ æ ~ .
~ o ~ O ~ o
10~ 3~
H 1~ u~ O l l
m
O Lr~ O I I
x m
~ O O * ~0
H ~~ N
H O O *
H V
X 1 11
H
X V~ Lr`~
H P:~ *
X
O 0 ~1
x mN ~ * ~0 1 1
U~ ~ O l I
X 1
H VH C~ r-l
~ 1 11
H 11~ 0 0 l l
H m ~ u~
_~~ V~1 ~ J o
I I ~ O
t.l H O Lr~
v~ m - u~ , N
i~i H~ m
11 o ~
H VtY) ~) H i i ~I ~;
H O O ,~
H Fq ~ Ir\ ¦ ¦ O
H V(Yl 11~ N~
¢ O O 1 o I I , 5,
H VN J r-l H
cJ
~ O O I I
H ¢ *
V
o o ~ No V ~ H14 i
~~ ~O +' O O ~ I I ~ ~ ~
~ ~o a) ,1 ~ ~ o ~ o
~0 ~~ O O rl C~ +~ I I
E~ ~ v~ d I I *
-- 23 --
~ .2_
~ .
