Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
36S86
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.~ The present invention relates to a process for the pre-
paration of synthetic lubricants as well as the lubricants obtained
; thereby.
:- According to the present invention, synthetic lubricating
~.: oils are obtained which have a high viscosity index, very low pour ;
.. ; point, low viscosity at 0F, considerable resistance to depolyme-
r.ization, high thermal stability, very low carbon residue and high
~lash point. ::
The process according to the present invention comprises .~ .
.. 10 two successive phases. ...
:,, . . :
... The irst phase has already been described in a copend-
,.. :; ing Canadian patent application No. 194,~96 of the same applicant `~
and concerns the preparation of polymers having considerably
. ~ high molecular weights and viscosities comprised ~ the range o e
,..
~ rom 250 to 15,000 cSt at 210F. Such polymers are obtained with
,.: high yields by polymerizing mixtures of alpha-olefines obtained .:
from wax cracking or of single normal alpha-ole~ines having the
. general ~ormula R-CH = CH2 wherein R is an alkyl radical contain-
ing from 2 to 16 carbon atoms, in the presence of a catalyst
formed by the complex TiC14/PIA (titanium tetrachloride/polyimi- `.-
noalane) and under an inert atmosphere possibly containing hydro-
~:: ,, - .. . .
gen up to a partial pressure of 1 kg/cm , and then by distilling .
the resulting product up to a head temperature of 175C.
The second phase of the process according to the pre-
.l sent invention consists in subjecting the above obtained polymers :.
.. having very high viscosities and boiling points higher than 175C,
to a catalytic cracking carried out at atmospheric pressure in ..
`.~. order to reduce the molecular weight thereof and to obtain thereby ::
. . . .
:~ oils having viiscosities comprised within the field oE lubricants.
.. 30 By means of such catalytic cracking, lubricating oils are
obtained which present high characteristics and particularly
~: improved thermal stability data.
,: . .
By suitably changing the type of catalyst used and the ..
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" . , , ~ , .. j " , .. . . . .
1~36~
operative conditions, such as temperature and space velocity,
oils can be obtained having any desired viscosities, from 4 cSt
up to 20, 30 or 50 cSt at 210F.
; In the catalytic cracking treatment, it is preferable
to use catalysts supported on carriers having a weak Lewis acidity,
such as the alumina type, for the purpose of obtaining as much as
possible a formation of low boiling products. The catalysts
advan-tageously used are those containing oxides or sulphides of
metals selected from the VI to the VIII group of the Periodical
System.
The variable factors of the treatment according to the
present invention are, using a defined catalyst, the temperature
and the space velocity. The useful temperatures are comprised
between 250 and 300C. The space velocity (~ISV), expreqsecl as
v/v/h, i.e., liquid volume per catalyst volume pex hour, ma.y
range from 0.1 to 5, preferably from 0.5 to 2.
The catalytic cracking treatment is carried out by
causing the polymer having a very high viscosity, which was ob-
,
tained in the first phase of the process, to flow at atmospheric
pressure through a tubular reactor electrically heated and con-
taining the catalyst. The resulting product is then fractionated
; at a reduced pressure up to a head temperature, referred to ;
atmospheric pressure, of 400C. The residue having a boiling point
higher than 400C constitutes the synthetic lubricating oil, the
j yield of which is calculated in percent by weight with respect
to the polymer having a boiling point higher than 175C used as
` feed.
When the viscosity oE the feed polymers is comprised
between 660 and 1150 cSt at 210F, the yields range respectively
from 61% to 57~ if oils having a viscosity of about 18 cSt at 210C
are produced and from 72% to 67~ if viscosities of about 30 cStare produced.
.
~ - 2 - ~ .
.
~ ~36S8~
The oil~ havin~ boiling points higher than 400C, obtai-
ned according to the above treatmentt are subsequently subjected
to hydrogenatio~ ~or eliminating the unsaturation present wherein,
; The h~dxogenation may be carried out according to con-
ventional and kno~n methods. In the present oase, it iB pre~era-
~; bl.~ ~arr~ed out in the pre~encè o~ a catalyst containi~g 0.3 % o~
Pd on alurnina~ at a temperature o~ 200C and under a starting
hydrogen pres~ure o~ 100 kg/cm 9 ~or a total time o~ 5 hours
~ he h~drogenated oil having a boiling point higher than
400C constitutes the synthetic lubricating oil o~ high ~uality.
;j.................... A h~drogenated oll, repre~entatire o~ the present inven-
tio~ ha~ing a risco~itg o~ abou-t 19 ¢St at 210~ pr4~en-~ a
viscosity inde~ o~ 130 i~ it i~ ¢alculat~d ac¢ordin~ to ~hc
AS~M D 227C/A me:thod and o~ 154 i~ i-t ls calculated according
to the method o~ ASTM D 2270~ ~ pour point o* -50C, considerable
depolymeri~ation resistan¢e, high thermic s~abilit~ ~ery low
carbon residue ana a ~lash point o~ 245C,
: The present invention will be better illustrated withm re~erence to the ~ollowing examples and accompanying tables~ ~hich
.
must not be considered as limiting the scope o~.the invention.
~; In the examples~the kinematic viscosities were determlned
according to the AS~M ~ ~45 method. The viscosity indices ~ere
. .
repor-ted by means o~ t~o values~ one which is calculated according
to the ~S~M D 2270/~ method and the other one according to the
ASrrM D 2270/B method~ the latter being pre~erred ~or vlscosity
indice~ higher than 100. 'rhe pour poin~ was determined aocord~ng
to the D 97 method and the iodine number accordi~g to the IP
84 me~hod~
EX~MP~E 1
; ~o A polymer ha~ring a boiling point higher than 175C and a
Yi~Cosity of 660 cS-t at 210~, obtained by polymerizing C8 - C10
.
. _ 3 _
. :
3658~
alpha-ole~ines ~rom wax cracking, was subjected to a catalytic
cracking carried out at di~ere~t temperatures~ in order to reduce
~: its viscosity and to obtain lubricati~g oilsO The treatme~t wa~
;i carried out by causing the polymer to ~low at atmospheric pressureand at a controlled speed -through a steel tubular ~4O^mm diameter)
. reactor electricall~ heated and contalning a catalytic bed consti-tuted by 200 cc o~ ac~ivated alumina having a content o~ 99 % .
Al2O3 (tablets 1/8"),
The resulting produc-ts were distilled under vacuum up
to a head temperature, reierred to atmospheric pressure, o~ 400QC.
'llhe residue heaving a boiling point higher than ~00 a consti tutea
the ~ynthetic lubricating oll,
'he re~ult~ are reportea ln tabl~ I~
From thesc re~ulbs~ ~ti~ apparent that ~rom the catalytic
cracking o~ a polymer ha~ing a viscosity o~ 660 cSt at 210~'~
lubr~cating oils ca~ be obtained even when operating at relative-
.~ ly low temperatures,
: It may be furthermore deduced that an oil havi~g a ris-
cosity of about 18 c~t at 21~~ can be obtained with a yield o~
; 20 about 61 ~o b~ weight, b~ operating at a temperature o~ about 268C
:~; and at a space velocity equal to 1,
. , EXAMPLE 2
~ ~he catalytic treatment was e~ected by using as ~eed
`........... polymer having a boil m g point higher than 175C a~d a viscosit~ .
o~ 1160 sCt at 210F7 which was obtai~ed by polymeri~in~ C8 - C10.
ole~ine~ f~om waæ cracking. ~h~ catalyst was the same a~ the one
; employ~d in example 1~ i,e,, 200 cc o~ acti~a-ted alumi~a containing
... 99 % Al203 (tablets 1/8").
'~he apparatus was equally the same as the one used in
.: 30 example 1,
~he results are repo.rted in table II,
.By examining these results, it was deduced that using
'`'' :
-'' ~ ,.,
36S8~ ~
.. ,., . , ~ .
~ as ~eed a polymer having a ~iscosity of 1160 cSt at 210~ lubri- ~
.. . . .
cating oils can be ob-tained by operating at a relatively low tempe~
; . rature. ;:
:. ~t m~y be ~urthermore deduced that ~n oil having a ~isco- `:
si-ty o~ about 18 cSt at 210~, could be obtained with a yield of
about 57 % by weight by operating at a space velocit~ equal to 1
~, and at a temperature o~ about 270C,
EX~P~E
The ~yn-thetic oil having a boiling point higher tha~
400C and obtained according to te~t 2 o~ example 2 (~ee table IX)
wa~ h~drogenatea in order to comple-tel~ saturate ~he ole~inic
double bonds present therein, '~he operatlon wa~ c~rried out ln an
autocla~e in the,pre~ence o~ a cataly~t con-ta~n~n~ OJ~ % Pd on
alumina~ a-t a temperature o~ 200C and under a hgdrogen pr~ssur~
o~ 100 kg/cm2~ ~or a total time o~ 5 hour~
The characteristics o~ the oil be~ore and a~ter hydroge~
nation are reported in table III.
.. . ..
- ~rom these results, it may be no~ted that the hydrogena- ~
,, .
tion did not substantially modify the characteristics o~ the oil
which remai~ed very good.
~ rom the values of the viscosity at 210~ and at 0~
as well a~ ~rom the pour points9 it is possible to deduce that
the oil would present a rer~ good behaviour ~ith ~espect to both
high and low temperatures.
;` A ve~y low value o~ the carbon residue and a high ~la~h
~, point were moreorer no-ticed.
. ~ .
.. . . .
; The hydrogenated oil o~ example ~ was subjected to tho
.
Raytheon shear ~ta~ility te~t with a ~onlo o~cillator ~or a t~me
. 3o o~ 15 minutes~ at a temperature o~ 100~ (AS~M D 2603-70),
The results were the ~ollowing:
.. ~ ;
;' 1, ' , '.
: 1 5
.. . . .. . . . .. .. . . . .
3~586
f
~s such A~ter test
Kinematic ~iscosity at 210~
-~ c~t 19.2 19~1
Kinematic viscosity at 100 F~
cSt 152 151
. _
By examining the above results9 ~t is apparent -that
the hydrogena~ed oil which was obtained accordi~ to the proce~s
o~ the present invention presents a good resistance to the sonic
depolymerization test,
; ~,~
, .
'.~he hydrogenated o~l o~ c~ample 3 wa~ ~ubjoc-ted to
thermic stab~lity te~t ac¢ord~ng to the m~thod o:~ thc ~ea~ral
Std~ n 2508 "r~hermal S-tabillty o~ ~ubrica~ing and Hydraulic
Pluids", which consists in ma~talning at a temperature o~ 260C
~i for 24 hour~ 20 cc o~ the oil under examination i~ a sealed gla~
tube,the oil being previously degased.
' ~'he resul-ts o~ the test were the ~ollowing:
; .,
. 20
.,
~ As suchA~ter test
;.~ Kinematic viscosit~ at 210~9
cSt 19.2 1901
Kinematic viscosity at 100~
cSt
; .. . ...
:`
~ From such results, it is possible to confirm that the
~ ...
oil obtained ac~ording~to the proces~ of the inventio~ ls ~herm~-
.; cally stable,
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