Note: Descriptions are shown in the official language in which they were submitted.
. 2
~L~57G8S
'rhe pre-sent invention relates to ca process ~or the preparation
~f lukri~itin~- oi.ls ~lith hi~h visco~,ity index by the catalytic
~drccrackin~ of a.rnixture of hravy hydroca.rbons, and to
lubricatin~ oils thus obta.ined.
For the preparation of lubricating oils with high viscosity
index, which among other purposes can be used as base oils for ;.
multi-grade lubricating oils, there are in princi.ple two routes
availabl.e, v~z.: the conventional route and ~he hydrocracking route, - ~;~
both of which are used on a commercial scale. :~`
The preparation of lubricating oils with high viscosity
index by conventional means is carried out as follows.~.
A waxy crude oil is separated by distillation at atmospheric .:.
. pressure into a number of distillate fra.ctions (to be specific~
one or ~ore gasoline fractions, Xerosine fractions and light
gas oil fractions in that order) and a residue (known as the long
I residue) This long residue is then separated by disti.llation
; under reduced pressure intc, a number of distillate fractions
Z (to be specific: one or more heavy gas oil fractions, spindle ;~:
I oil fractions, li~ht machine oil fractions and medium heavy
,~. 20 machine oil fractions in that order) and a residue (known as the
short resldue). From the lubricating oil fractions obtained during
the distillation under reduced pressure the correspondin~
lubricating oils are prepared by re~ining. The refining of the
~, spindle oil fractions, li~t machine oil fractions and medium
'! 25 heavy machine oil l~ractions is achieved by removal of aromatlcs
.~ and paraffi.n waxes from these fractions. ~he removal of aromatics
and pa.ra.ff.in waxes from the lubricatirlg oil fractions can be
,! ~
./ , ~
~13 57G8S
carried out in random sequence. In order to keep the volume of
oil to be dewaxed as small as possible, it is preferable to
; first remove the aromatics and then the parafin waxes. In this ~ ~
; manner the corresponding wa~y raffinates and subsequently the ~ ~;
corresponding finished lubricating oils are prepared from the
spindle oil3 light machine oil and medium heavy machine oil
waxy distillates. In the refining of the short residue~ asphàlt
is initially removed from the residue. Aromatics and paraffin ~ ;
waxes are then removed from the de-asphalted oil thus obtained.
~i 10 In this manner first the brightstock waxy raffinate and subse-
`1 quently the finished brightstock are obtained from the de-asphalt- ;
ed oil. The paraffin waxes obtained during the refining of the
various lubricating oil fractions are referred to as slack wax.
! The preparation of lubricating oils by hydrocracking is
t carried out as follows. A heavy fraction of a waxy crude oil,
- such as a vacuum distillate, a de-asphalted oil or a distillate
~: .
~ of a residual slack wax is passed over a suitable hydrocracking
,"!' catalyst at elevated temperature and pressure and in the
presence of hydrogen. One or more lubricating oil fractions
are separated by distillation from the hydrocracked product.
From the lubricating oil fractions thus obtained the
;xl correspondlng lubricating oils are prepared by removal o-f
paraffin waxes from these fractions. Just as in the con-
ventional preparation of lubricating oll~ the paraffin waxes
1 obtained during the preparation of lubricating oil by hydro-
`~ cracking are referred to as slack waxO
,;,. ~ ~
'.:! .
. .
.
i -3-
.;, .
... ...
~05r76~i
The dewaxing of lubricating oil fractions can be
effected by cooling, upon which the paraffin waxes s~para~e
out as solids and can be filtered off. The dewaxing is
preferably carried out by cooling in the presence of a solvent~
Suitable sol~ents for this purpose are, among others, mixtures
of a ketone such as acetone~ methyl ethyl ketone or methyl iso~
butyl ketone ~ith an aromatic compound such as ben~ene, toluene
or xylene. In practice large-scale use is made of a mixture of
methyl ethyl ketone and toluene for this purpose~ The dewaxing
of lubricating oil fractions in the presence of a solvent is
effected by mixing the waxy lubricating oil fraction with the
so~vent and heating the mixture to a temperature that is about
20-30 C higher than the temperature that is necessary for the
complete dissolving of the paraffin waxes. The solution is
then slowly cooled to the filtration temperature, which is ~;
generally about -20 to -30C.
After washing the fllter cake with solvent that is at
the filtration temperature and removal of the solvent from the
filtrate and the filter cake the dewaxing is ready~ In ~ ~
this way~ in addition to a dewaxed lubricating oil~ a slack `
wax is obtained which latterg in addition to a mixture of
paraffin waxes with various structures and melting points~
I still contains a considerable quantity of oil. Distillate
I paraffin waxes and residual paraffin waxes are prepared from this
slack wax by de_oiling. `
Distillate paraffin wax is prepared by de-oiling of slack
wax obtained during the dewaxing of light and medium hea~y `
!
~35~
distillate lubricating oil fractions. Residual paraffin
wax is principally prepared by de-oiling of slack wax obtained
during the dewaxing of residual lubricating oi], fractions.
On the basis of their composition, residual paraffin waxes
are differentiated into ~P wax and microwax
The de-oiling of ~lack wax in the preparation of dis-
tillate paraffin wax can be effected by melting the slack wax~
casting the melt in a thin layer and cooling ~he latter slowly
so that the slack wax solidifies again. By slowly heating up
the solid mass~ ~he paraffin waxes with the lowest melting points
melt and dissolve into the oil that is present as free oil between
the paraffin wax crystals. This causes the liquid content of the
solid mass to rise. Eventually the liquid content of the solid
mass reaches such a level that the liquid can no longer remain
adsorbed between the paraffin wax crystals and separates from
the solid mass. This sweating, as it is knowng of the slack wax
is continued until'the remaining paraffin wax (distillate paraffin -~
. ~i .:
wax) has the desired low oil content. Since low-melting point
paraffin waxes - rich in branched paraffins - are removed along
with the oil~ the remaining distillate paraffin wax has a lower
'' branched paraffin content than the original slack wax. The
,,, mixture of oil and low-melting point parafin waxes obtained
during the de-oiling of slack wax in the preparation of
I distillate parafein wax is reerred to as foots oil.
,1 ~ The de-oiling of slack wax in the preparation of res-
idual paraffin wax is effected in the presence of a solvent.
~1, This method is also very suitable for ~he preparation of distillate '
:' " . ;
,' ' :
6~ ~
paraffin wax. Thc same solv~nts can be used for de-oiling as
are used for the dewaxing of lubricating oil fractions.
Just as in dewaxing~ for de-oiling large-scale use is made
in practice of a mixture of methyl ethyl ketone and toluene.
The de-oiling of slack wax in the presence Qf a solvent in
the preparation of distillate and residual paraffin wax is
effected by miæing the slack wax with the solvent, heating ~he
mixture until the waxes have dissolved and then slowly cooling
the mixture to the filtration temperature. After washing the
filter cake with solvent that is at the filtration temperature and
i removal of the solvent from the filtrate and the filter cake de-
oiling is ready. In this way, in addition to a distillate or
residual paraffin wax~ a foots oil is obtained which latter con-
tains a mixture of paraffin waxes in addition to the oil origin-
ally present in the slack wax. If the de-oiling is used for the
preparation of distillate paraffin wax from slack wax~
the mixture of paraffin waxes present in the foots oil consists
.i , ,
largely of low-melting point branched paraffins. If the de-oiling
:, :
is used for the preparation of residual paraffin waxes~ the
; 20 mixture of paraffin waæes present in the foots oil consists
largely of low-melting-point branched paraffins and cyclo-
i paraffins.
, The de-oiling of slack wax can be carried out in two
stages, it being possible to obtain two different qualities `
of paraffin wax from one slack waæ. For this purpose either
the para~fin wax or the filtrate from the de-oiling must
be subjected to an additional treatment. Using the route in
6~
~ , .
., . ~
- 7 ~ 105'~6~i
~l~ic~ t~e paraffin waxes are ~ubjected to an additional
process, the de-oilin~ ol the slack wax with solvent is e~fected
in the first stage of the process at a lower temperature and
the treatment of the separate~ paraffin wax with solvent
in the second stage of the process at a hi~her temperature.
At this higher temperature only part of the paraffin wax
crystallizes out. The lower-melting point paraffin wax
can be produced from the filtrate from the second stage by
removal of the solvent. In this process the foots oil is isolated
from the filtrate of the first stage by removal of the solvent.
Using the route in which the filtrate f`rom the de-oiling is
subjected to the additional treatment~ the de-oiling of the slack
wax is effected with solvent in the first stage of the process
at a higher temperature. In this case only the higher-melting
point paraffin wax crystallizes while the lower-melting point
~; paraffin wax remains in the filtrate. If the filtrate from
I the ~irst stage is cooled to a lower temperature~ the lower-
melting point paraffin wax separates out. In this process the
foots oil is produced from the filtrate of the second stage by
removal o~ the solvent. Fractionated de-oiling is used on a
large-scale in practice for the preparation of both HMP wax
; and microwax from a slack wax derived from a residual
.. . .
! lubricating oil fractlon.
`, The foots oil referred to on a number of occasions
in the foregoing, which is obtained in considerable quantities
3 as a by-product Or the preparation on a commercial scale of `~
I di~tillate and residual paraffin wax by de-oiling of slack wax,
.,
t7~
.
has so far been used as a blending component in fuel oil and in feeds ~ -
for catalytic cracking plants~ Where mention is made of foots oil ln
this patent application this shall be understood to mean a mixture of - -
oil and paraffin waxes obtained as a by-product in the preparation of
..
distillate or residual paraffin wax by de-oiling of slack wax.
It has now been found that foots oil as such or ln mixtures
with other heavy hydrocarbon fractions is particularly suited to serve
as starting material for the preparation of lubricating oils with high
` viscosity indexes by catalytic hydrocràcking.
; 10 The present invention therefore provides a process for the
preparation of lubricating oils with high viscosity index by the hydro-
, cracking of a mixture of heavy hydrocarbons, characterized in that amixture of heavy hydrocarbons consisting at least partially of one or
more foots oils (a foots oil being a mixture of oil and paraffin waxes
obtained as a by-product in the preparation of distillate or residual t
paraffin wax by de-oiling of slack wax) is contacted in the presence of
hydrogen with a catalyst that contains one or more metals of Group VIB,
VIIB or VIII supported on a carrier composed of one or more oxides of
elements of Group IT~ III or IV, at a temperature of 325C-450C, a
, 20 pressure of 10-250 bar, a space velocity of 0.2-5.0 kg of feed/l of `~ ;
catalyst/hr and a hydrogen/feed ratio of 100-5000 Nl hydrogen/kg of
feed.
If for the preparation of lubricating oils according to
the invention a feedstock is used that is obtained by mixing one or
more foots oils with one or more other heavy hydrocarbon fractions,
, for this purpose use is preferably made of heavy hydrocarbon fractions
j selected from the group formed by
`l a) waxy lubricating oil fractions obtained during the distillation
1 ~ ~
,
:, :
.; :
~.
- 9 ~ S'~5
under reduced pressure of atmospher:ic distillation residues of
waxy crudec~
b) sla.ck waxes that have been separated from the waxy lubricating
oil fractions referred to under a), ~,
5 c) slack waxes that have been separated from waxy lubricating
oil fractions obtained by hydrocracking, and
d) mixtures Or two or more of the heavy hydrocarbon fractions
referred to under a), b) a,nd c). Examples of' such heavy hydrocarbon
fractions are spindle oil, light machine oil and medium heavy ,
, 10 machine oil waxy distillates and de-asphalted oils, the corresponding : . ~
waxy raffinates that have been obtained from the above-mentioned ,:
lubricating oil fractions by processingr with a. selective solvent
for aromatics such as furfuralS a,nd the corresponding slack
~: waxes that have been obtained from the above-menti.oned 1ubri.cating ~ .,
' 15 oil fractions by dewaxing. Mixtures of one or more distillate
,l lubricating oi]. fractions and/or one or more residual lubricating
;' oi.l fractions and/or one or more slack waxes ca.n also very suita.bly
be used together with one or more foots oils as starting materia.l ~'
~ for the ~reparation of lubricating olls with high viscosity index
,`, 20 according to the invention.
! If for the preparation of lubricating oils according , ~,
to the invention a mixture of two or more .foots oils is used ,
! .
~, as feedstock, use can very suitably he made of foots oils
-~ that have been obtained by dewaxinÆ and slack wax de-oiling from ~ ,'
:~, 25 lubricating oi,l fractions the boi.ling ranges of which are
substantially similar or substantiall.y contiguous to each
other. Thus, for example, use can very suitably be made of
` ~"`
,1 .
'', '
,
.~, , ~'
~ ` .
Y~35 : -
a mixture of foots oils that have all been obtained from light
and/or medium-heavy distillate lubricating oil fractions or from
heavy distillate and/or residual lubricating o:il fractions by
dewaxing and slack wax de-oiling. A similar situation applies if
for the preparation oP lubricating oils according to the inve~tion
a feedstock is used that has been obtained by mixing one or
more foots oils with one or more other heavy hydrocarbon
fractions. As blending components for th~ foots oils use can very
suitably be ~ade of lubricating oil -fractions or slack waxes
obtained ~herefrom by dewaxing, which lubricating oil fractions
have a boiling range that is substantially similar or substantially ~ -
contiguous to the boiling range of the lubricating oil fractions
from which the foots oils were obtained by dewaxing and slack
wax de-oiling. Thus~ for example~ one or more foots oils
obtained by dewaxing of light and/or medi~n heavy distillate `~
lubricating oil fractions and slack wax de-oiling can very suitably
be mixed with one or more light and/or medium~heavy distillate ~;
lubricating oil fractions or with one or more slack waxes ob_
!1 tained therefrom by dewaxing. One or more foots oils obtained
by dewaxing;of heavy distillate and/or residual lubricating
oil fractions and slack wax de-oiling can also very suitably be
. mixed with one or more heavy distillate and/or residual lubri-
- cat mg oil fractlons or with one or more slack waxes obtained
therefrom by dewaxing.
A very suitable starting material for the preparation of
lubricating oils according to the inventlon is a mixture of one
or more foots oils and one or more slack waxes, both the foots
oils and the slack having been obtained from lubricating oil
; ", , , ., . , ~ , . , ,;, , .. ,. ,, .. .. .. ... -: , ~
~V576~35i
rractions the boili.n~ ranges of whi ch are substan~,ially simi.lar
or subst;)n~ially contig~ous to each other.
When USill~r a mixture o.~ one or more foots oils with one
or more s1.ack waxes as starting materi.al for the preparation Or
lubricatin~ oi.ls according to the invention, it may be advantageous :
for the mixture to be partially composed of one or more foots
oils and/or slack waxes derived from lubricatin~, oil fractions that
have been prepared by conventional methods, the remainder comprisin~
one or more foots oils a.nd/or slack waxes derived from lubricatin~
oils fractions that have been obtained by hydrocracking. An example
. of such a starting material is a mixture consisti.ng of the
. followin~ five components:
~ a) a foots oil obtained by de-oiling a bri~htstock slack wax
y which latter was prepared by dewaxin~ a brightstock waxy raP~i~ate,
, 15 b) a slack wax obtained by dewaxing a lubricating oil ~raction,
i~ which latter was prepared by hydrocracking a de-asphalted oil, ~.
!~ c) a slack wax obtained by dewaxing a brightstock waxy raffinate,
~ d) a.slack wax obtained by dewaxing a lubricating oil fraction
i which latter was prepared by hydrocracking a medium heavy machine :~
oil waxy distilla.te, and
, e) a slack wax obtained by dewaxin~ a. medium-heavy machine
oil waxy distillate.
For the preparation of lubricatin~; oils according to
J
the invention use is ~4~ made of a catalyst that contains
one or more meta1s of Groups VIB, VIIB and/or VIII supported
I on a carrier composed of one or more oxides of elements of
¦ Groupg II, III and/or IV, ~xamples of ~uitable metals are
:J . ~ :~
:~ :
,,
:~.
- l2 ~ ~3~76~S
nickel, cobalt, molybdenum and tungsten. Preference is ~iven
to catalysts that contain at lea;t one metal that has been
sclected from the group comprisi.rlg ni.ckel a.nd ~obalt and at
least one metal that has been selecteci from th~ ~roup
compri.sing ~olybdenum and tun~sten. The metals may be present
on the carrier as such or as metal oxides or metal sulphides.
The catalysts a.re preferably used in the sulph;dic form. :.
Sulphiding of the catalysts may be ef~ected accordin~ to
any process known in the art for sulphiding catalysts, for ~;
example by contacting the catalyst with a mixture of hydrogen ;:.
and hydrogen sulphide or with hydrogern and a sulphurous ~
hydrocarbon oil such as sulphurous gas oil. ~ ~:
Examples of suitable carriers for the catalysts that
may be used according to the present invention are silica,
alumina, zirconia and magnesia; a.nd also mixtures of these
oxides, such as silica-alumina, silica~ma~nesia and silica-
zirconia. Preference is given to catal.ysts that contain alumina .
as carrier materia.l.
Catalysts are used according to the present inventîon ~ :
may also contain promotors such as fluorine, boron and/or
phosphorus. Fluorine may be incorporated into the catalysts -
durin~ any sta~e of the catalyst preparat.;on. Fluorine may
also be incorporated into the catalysts by fluoriding the la.tt.er
in situ. In-situ fluoriding of the catalysts may be effected
by adding, during the initial phase of the hydrGcra.cking
process, a certain quantity of a fluorine compound ko the
gas and/or liquid stream that is passed over the catalyst,
e .
;~
; ~
" ~ , .
S~ 5
~ntil the required ~luorl ne content of the catalyst is
attained
For the preparation of lubr;cating oils according to
the invention one of the rollowing t~o type~ of catalyst is
preferab]y used (A and ~):
A. A f]uorine-containing nickel-tungsten catalyst on alumina
as carrier, which catalyst has a compacted bulk density o~
at least o.8 g/l, contains at least 3 parts by weight ~;
of nickel and 20 parts by weight of tungsten, respectively,
per 100 parts by weight of carrier and has been prepared
as follows from an alumina hydrogel from which, by drying
`` and calcining, a xerogel with a compacted bulk density
of less than o.8 g~ml can be obtained:
1) If the pore volume quotient (as defined herein after) of the
said xerogel is at least 0.5, the preparation of the catalyst
takes place either
a) by drying and calcining the alumina hydrogel,
incorporation of the metals and, if desired, fluorine into the
xerogel, and drying and calcining of the composition, or
b) by incorporation of the metals andj if desired, ~luorine
into the alumina hydrogel and drying and calcining of the com-
J position.
2) If the pore volume quotient of` the said xerogel is less
than 0.5, the preparation of the catalyst takes place by
~j 25 incorporation of the metals and at least part of the fluorineinto the alumina hydrogel and drying and calcining of the
~ composition provided that in the latter case fluorine is
.
' ~:
s
incorporated :into the alumina hydroge:L in sufficient quantity
that from this f1uorine-containing alumina hydrogel a xerogel
with a pore volume quotient of at least 0.5 can be obtained ;
by drying and calcining.
In this patent application by the pore volume quotient
of a material shall be ~derstood the ~uotient of the mercury
pore volume and the total pore volume,.of the matericil, the
mercury pore volume being defined as the pore volume present in
pores with a diameter greater than 7.5 nm determined with mercury
and the total pore volume being defined as the to~al of the pore
volume present in pores wi.th a diameter of less than 60 nm deter- ~
mined with nitrogen and the pore volume present in pores with.a ~ ;
diameter of at least 60 nm determined with~mercury.
B. A fluorine-containing nickel-tungsten catalyst on a carrier
in ~hich catalyst at least part of the fluorine has been incor- ~:
i - porated by in-situ fluoriding. ::
¦ The hydrocracking of foots oils or of a mixture of one --
j or more foots oils with one or more other heavy hydrocarbon frac-- .
.~ tions in the preparation of hlbricating oils with high viscosity
index according to the invention is effected by contacting the
feed at elevated temperature and pressure and in the presence of
hydrogen with the catalyst, which is preferably present in one or
`l ,
i more beds of particles with a si~e of between 0-5 and 3 mmO
~ Suitable hydrocracking conditions are~ a temperature of ~ -
-} 325-450 C, a pressure from 10 to 250 bar, a hydrogen/feed ratio
j of 100~5000 N1 hydrogen per kg of feed and a space velocity -~
~ of 0.2-5 kg of feed/l of catalyst/hour. It is preferably to use ;~
::3 -~
~-~
... .
_~ ~5ty~
the following conditions: a temperature of 350-425C~ a
pressure of 40-200 bar, a hydrogen/feed ratio of 500~2500 Nl
hydrogen/kg of feed and a space velocity of 0.5-1.5 kg of
feed/l of catalyst/hourO
Lubricating oils prepared according to the inven~ion
have a low aromatic content. Lubricating oils with an even
lower aromatic content can be prepared according to the
invention if the hydrocracking step is followed by a hydro- ;
finishing step~ Hydrofinishing of the hydrocracked product
can be carried out by contacting the hydrocracked product
at elevated temperature and pressure and in the presence of
hydrogen with a hydrofinishing catalyst. The pressure,
space velocity and gas velocity that are used in the hydro-
finishing step may be selected within the same limits as
give above for the hydrocracking step. The hydrofinishing ~-
temperature is preferably selected between 225 and 400C and
particularly between 275 and 375 C. The temperature applied
in the hydrofinishing step should be at least 25C lower than
the temperature at which the hydrocracking step is carried out.
Suitable hydrofinishing catalysts are catalysts that contain
one or more ~etals of Groups VIB~ VIIB or VIII on a carrier.
The effluent from the hydrocracking reactor~ or~ if
hydrofinishing is usèd, the effluent from the hydrofinishing
r0actor~ is cooled and separated into a hydrogen-rich gas
and a liquid product. The liquid product comprises hydrocarbons ~-
that boil below the boiling range of lubricating oils and ;~
hydrocarbons that boil within this range. The hydrocarbons
j ~` "
`~
.1
~ ~ ~t~ ~ 8
that boil below the said range are separated from the higher ~ ,
boiling residue, preferably by fractiona], distillation. The
cutting point of this distillation is preferably selected
such that the higher boiling point residue has an initial
boiling point :in the region of 350-550C. In addition to ~ ;
excellent lubricating oil components3 this residue generally
contains paraffin waxes that solidify at ambient temperature and
therefore adversely affect the pour point of the lubricating oil. ~ ~'
In order to obtain a suitable lubricating oil from the residue,
it is therefore preferable to dewax this residue. The dewaxing
process may be effected in any desired manner. The dewaxing is
preferably carried out with a mixture of methyl ethyl keton~ and toluene
, at a temperature between -10 and -40C and a solvent/oil
volume ratio between 1 : 1 and 10 : lo In order to increase
! the yield of lubricating oil it is preferable to recirculate
at least part of the separated paraffin waxes to the hydro~
~ cracking reactor.
Il The invention will now be elucidated by reference to
'-~, the following Examples. In these Examples use was made of
~ 20 three feeds (I-III) and two catalysts (A and B).
.
FEED I
; Oil obtained by de-asphalting a residue derived from the
'l distillation under reduced pressure of an atmospheric
diStillation residue of a Middle East crude. This de-
asphalted oil had the following properties:
VI after dewaxing at -30 C: 77
sulphur content: 201% by wt.
~ , ,.
~ nitrogen content: 630 ppmw. , '
'' -16-
:. ,
- 1 7 ~ 7~85
FEED II
,:.
Foots oil obtained by de-oiling a brightstock slack wax.
The slacl~ wax was prepared starting from the de-asphalted oi]
described above as f~eed ~ by ex~!raction with rurfural rol]owed
by dewaxing of the brightstock waxy raffinate with a
mixture of methyl ethyl ketone and toluene at a temperature of
-20C. The yield of brig,htstock slack wax was 15~ by weight
expressed in terms of de-asphalted oil. The de-oiling of the
bri~htstock slack wax was carried out in two stages usin~
a mixture of methyl ethyl ketone and toluene as solvent.
In the first stage of the de-oi~ing process the slack wax
was dissolved in the solvent at elevated temperature and the
mixture was then cooled to 42C, The crystallized HMP wax
was then washed with so]vent of 42C and the solvent was
removed from the HMP wax. In the second stage of the process
the filtrate from the first stage was cooled to 11C.
The crystallized microwax was washed with solvent at ll~C
and the solvent was removed from the microwax. The foots oil
was obtained from the filtrate of the second stage by removal
~, 20 of the solvent~ In this manner 100 parts by weight of bri~,htstock
sIack wax yielded:
11 parts by wt of EIPM wax with a setting point oE
86,5C,
40 parts by wt of microwax with a settin~ point
~ 25 of 58~C, and
¦ 49 parts by wt of foots oil.
I This foots oil had the following properties:
.' ~
:, ~
. !
':
', . ` ', ' , ' ,:
~ L)S7~1!35
nitrogen content: 214 ppmw
sulphur content: o.8s% by wt
paraffin wax content (deter-
mined at -30 C3: 62.5% by wt
Oil content (determined at
_30C): 37.5% by wt
This oil had the following properties~
V ". ', '
k210 35.3 cS
VI: 101 ~ ~
Pour point: -20 C ~ ~`
FEED III
A mixture with the following composition~
12.5% by wt of foots oil ;
3205% by wt of slack wax obtained during the dewaxing of
a lubricating oil that was prepared by hydrocracking a,
de-asphalted oil ~ ;
9% by wt of slack wax obtained during the dewaxing of a
brightstock wax~ raffinateO 17.5% by wt of slack wax ~ `
,
i obtained during the dewaxing of a lubricating oil that
was prepared by hydrocracking a medium-heavy machine oil
wax~ distillate.
28.5% by wt of slaok wax obtained during the dewaxing - ;
of a medium-heavy machine oil waxy raffinate.
This mixture had the following properties~
nitrogen content: 32 ppmw
sulphur content: 0.3i~0 by wt `~
~i paraffin wax content (determined at
s _30C): 69.o% by wt `~
' ~ .
-18-
6~35
oil content (determined at -30 C): 31~0% by wt
This oil had the following properties: ~ f
Vk210: 23.5 cS
VI: 99
pour point: -21C
The foots oil included in thi.s mixture was prepared
by de-oiling a brightstock slack wax obtained during the i;
dewaxing of a brightstock waxy raffinate from a Middle East
crude. The de-oiling was carried out in two steps in the same
manner as described for the preparation of the foots oil
used as ~eed II. In this manner lO0 parts by weight of brightstock
slack wax yielded~
9 parts by wt of HPM wax with a setting point o~
86.5C~
35 parts by wt of microwax with a setting point
of 58Cj and ;"~
~ 56 parts by wt of foots oil~
,~ Thi foots oil had the following properties~
nitrogen content- 130 ppmw
sulphur content: 1.04% by wt
I ~B paraffin wax content (determined
fj at -30 C): 4401% by wt
oil content (determined at -30C): 5509% by wt
- This oil had the following properties~
k ~ ~ i
210: 36.o cS
1~ YI: 99
iff Pour point- -21 C
- 9
., ' .
CATALYST A
This catalyst, which contained 37 parts by weight of nickel
70 parts by weight oftungSten and 14 parts by weight of fluori~e
per 100 parts by weight of alumina, carrier and had a compacted
bulk density of 1.2 g/ml, was prepared starting from an alumina
hydrogel from which a xerogel could be obtained with a compacted
bulk density of 0.35 g/ml and a pore volume quotient of o.8 by
drying and calcining. The preparation was efected by mixing ;
an aqueous solution that contained a nickel compound, a tungsten
compound and a fluorine compound~ with the alumina hydrogel
and keeping the mixture at elevated temperature for some time~
separating the hydrogel loaded with metals and fluorine from
the mixture and subsequently drying, extruding and calcining ~`
the hydrogel.
CATALYST B
This catalyst, which contained 10 parts by weight of
~` :
nickel, 20 parts by weight of mo~enum~ 2 parts by weight
of phosphorus and 2.5 parts by weight of fluorine per 100 parts by
weight of carrier, was prepared by impregnating an alumina
carrier with an aqueous solution that contained a nickel ;~
compound~ a mo~d~num compound and a phosphorus compound~
followed by drying and calcining the composition. FluDrine
was incorporated into the catalyst by in situ fluoriding.
Catalyst A was used for the preparation of lubricating
oils with high viscosity index by hydrocracking feeds I
and IIo The catalyst was used in s`ulphided formO The
-20-
~ 21 -
~ 057~35
sulphiding of the catalyst was carried out by contacting
the latter for 5 hours with a mixture of hydrogen and
hydroger. sulp~ide in a ratio by vol,ume of 7 : 1 at a
tc~perature between 75C and 375C and a pressure ol' 10 bar.
The catalyst was used in th~ form of 1.5 mm extrudates. The
, hydrocracking was carried out under the follo~rin~ conditions:
~ hydrogen partial pressure 150 bar
,~ space velocity: 1 l.l l,hr 1
hydrogen/feed ratio: 2000 Ml.l 1 ;
Thç results of these experiments a,re given in Table A.
TabI _A
, Ex~eriment No. 1 2_ ~ 4
~ Feed ~ , I II II II
'', H~drocra_kin~ tem~erature~ C 410 380 385 395
~-~ Yield of 390C fraction
`' based, on feed~ % b~ wt__ _ ___ __8. 1~I __22.____ __50 0
Prop~,rties of the 390C
~raction after dewaxin~ at -30C ~,~
~! Yield based on feed,
;, % by wt 3 36.6 39.5 3~.0 '
'j'! k210~ Cs 14.9 12.4 B.5 ~ ,
, VI 140 124 127 l4n
, ' Pour point, C -18 -18 -20' -21 ;'
,, _____________________________~____ -----------------------'!--------- l
'', Experiments 2, 3 and 4 shown in ~able A are experiments ~"
~l according to the invention. Experiment 1 ~alls outside t,he '
'~ scope of the invention and has been included for comparison.
.. ' ' ~
- ,
'
' :,
. .
~0~'7~;~3S . ~
~ comparison of the results of experiments 1 ~nd 4 shows
that foots oils is a more attractive base material for the
preparation of lubricating oils with high viscosity index
by hydrocracking than the de-asphalted oil from which this
foots oil has been derived. In both cases a lubricating oil is
obtained with a viscosity index of 140; however, when foots
oil is used as feed~ a higher yield of this lubricating oil
is obtained and moreover the lubricating oil has a higher ;
viscosity.
From the results of experiments 3 it is apparent that
the product obtained has a higher oil content than the feed
used as starting ~aterial, while the viscosity index of the
oil in the product ~VI 127) is 26 points higher.
An even higher viscosity index is obtained accordiMg to
experiment 4 ¦VI 140)~ but at the expense of a small loss in
yield. A comparison of the results of experiments 2 and 4 shows
the advantage of the higher hydrocracking temperature. In both
experiments approximately the same yield of lubricating oil is
obtained; the lubricating oil prepared at the higher hydrocracking
temperature, however, has a VI that is 16 points higher.
E~AMPLE II
Catalysts A and ~ were used for the preparation of
lubricating oils with high viscosity index by hydrocracking
feed III. The conditlons relatin~ to sulphiding of the
catalysts were the same as given in Example 1. The hydro~
cracking was carried out under the following conditions~
-22- ~
`:
. .
hydrogen partial pressure: 130 bar
space velocity: 1 ~g.1. l.hr-1
Hydrogen/feed ratio: 1500 Nl.kg 1
The catalysts were used in the form of 1.5 mm extrudates. .
In-situ fluoriding of catalyst B was effected by adding 300
ppmw of fluorine as ortho-fluorotoluene to the feed during the
initial phase of the experiment until the required fluorine
content of the catalyst was attained.
The results of these experiments are given in Table Bo
- . ~ . ~, . , . , , . :
7~S ~:
O H ~ i-' ~ O I tD
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c~O ~ Dq ~ t ~
~b ~
3 ~ g
o ~ ~ , lo
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$~ lw lo
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.: ~`: `
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- 2 4 -
, ., :-~
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~L~VS fi'~35
The results of experiments 5-10 given in Table B show the
suitability o~ foots oil as a component in a mixture of heavy ,
hydrocarbons from which lubricating oils with high viscosity ~ -
index can be prepared by catalytic hydrocracking.
A comparison of the results of experiments 6 and 9
shows ~hat catalyst A is more suited to the present purpose
than catalyst B. In both experiments a lubricating oil is
obtained with substantially the same viscosity and viscosity
index. When using catalyst A~ however, a higher yield of this ~,
lubricating oil is obtained and moreover at a lower hydro-
cracking temperature.
,., ~::
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-25~
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