CA1036586A - Synthetic lubricating oils from catalytic cracking of polymers of a very high viscosity - Google Patents
Synthetic lubricating oils from catalytic cracking of polymers of a very high viscosityInfo
- Publication number
- CA1036586A CA1036586A CA194,659A CA194659A CA1036586A CA 1036586 A CA1036586 A CA 1036586A CA 194659 A CA194659 A CA 194659A CA 1036586 A CA1036586 A CA 1036586A
- Authority
- CA
- Canada
- Prior art keywords
- viscosity
- catalyst
- process according
- volume
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 10
- 239000010689 synthetic lubricating oil Substances 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract 2
- 239000011261 inert gas Substances 0.000 claims abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 20
- 239000000314 lubricant Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BGRJTUBHPOOWDU-UHFFFAOYSA-N sulpiride Chemical compound CCN1CCCC1CNC(=O)C1=CC(S(N)(=O)=O)=CC=C1OC BGRJTUBHPOOWDU-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/007—Soaps or soap mixtures with well defined chain length
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/02—Compositions of detergents based essentially on soap on alkali or ammonium soaps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Synthetic lubricating oils are obtained by subjecting a polymer having a viscosity in the range of 250 to 15,000 cSt at 210°F and a boiling point higher than 175°C, prepared by polyme-rizing normal alpha-olefines having t?? general formula R-CH = CH2 wherein R is an alkyl radical containing from 2 to 16 carbon atoms, in the presence of a TiCl4/polyiminoalane catalyst and in an atmosphere of an inert gas and/or hydrogen having a hydrogen pressure of less than 1 kg/cm2, to a catalytic cracking carried out at atmospheric pressure and at a temperature of from 250 to 300°C, the volume of liquid per volume of catalyst per hour being com-prised between 0.1 to 5, distilling the resulting product under vacuum up to a head temperature, referred to atmospheric pressure, of 400°C and subjecting the residue having a boiling point higher than 400°C to a catalytic hydrogenation. The oils produced by this process have a high viscosity index, very low pour point, low viscosity at 0°F, high thermal stability, high resistance to depolymerization, high flash point and very low carbon residue.
Synthetic lubricating oils are obtained by subjecting a polymer having a viscosity in the range of 250 to 15,000 cSt at 210°F and a boiling point higher than 175°C, prepared by polyme-rizing normal alpha-olefines having t?? general formula R-CH = CH2 wherein R is an alkyl radical containing from 2 to 16 carbon atoms, in the presence of a TiCl4/polyiminoalane catalyst and in an atmosphere of an inert gas and/or hydrogen having a hydrogen pressure of less than 1 kg/cm2, to a catalytic cracking carried out at atmospheric pressure and at a temperature of from 250 to 300°C, the volume of liquid per volume of catalyst per hour being com-prised between 0.1 to 5, distilling the resulting product under vacuum up to a head temperature, referred to atmospheric pressure, of 400°C and subjecting the residue having a boiling point higher than 400°C to a catalytic hydrogenation. The oils produced by this process have a high viscosity index, very low pour point, low viscosity at 0°F, high thermal stability, high resistance to depolymerization, high flash point and very low carbon residue.
Description
' :
.~ 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 ..
.`'. ' ' ' ~ , " . , , ~ , .. 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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- 8 -- :.
.~ 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 ..
.`'. ' ' ' ~ , " . , , ~ , .. 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, ,'. ;:,:
.... .
. ,' , ! - 6 -''...................................................... ' ;
., . . . .. . ; . .. .
. . . . . . . .. . . .. . . . ... ... ... . . . .... . . ..
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.. .p~:l E I V~ ~-- 1~ ~0 ) ~:1 H ~ ~ O CO ..
.. i~ H O ~J ~~_ c~ O C~ C~l It~ -- CO ~:
.,, P~ ~ . Pl ~
. ~. 00 0 r- . ~ ~ ~ r- oo ~i ' ~ . ~ ,Q r-- ~ 1~ ~1 ~ 0 U~ ~t ~, .
~ ~ . U~ ~ ~ ~ O O O
.. tl ~1, C~ 1~ ~ L~
.: ~ o a) V O (1) V N C~ l :`:
E~l o . . H O
U~, p U~
~ N
'j , ' . ` 1'~
.~ ~ ... .
, ; ~
:
:
~ ~ 36586 CO C~l o Otl~ O 0'~ N O ~ L~
H ~ ~ L~ t~1~ 0 Lf~
: ~ r~ :
,, ~
. ~ ~I
i'' Pi .,~ .
~ ~ .
el +~
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: cr; o a) . , ~ h O 00 a~ O N O
O ~ ~ tt~ 0 1 1 1 1 ~ r ~c~ ,i I~
., ~ g .
. N ~2; ,.
. ' '~ ll H ~i . ~ .
¢1 '~ ~ d N N ~D1~ C~J N
O t-- ~ d N N N a~
I:q C~l ~d P F~ R Q Rl ~
. E~ E I ~ i~
, ~ ~ U~ 11 ~;,. O ~ ct~Cc ~ cq ~ cqcl c~ cq O H .~
:. H . . .
,,,,,,, j~ ' V ~ , ;i ,., . o~ C) C~ ov ~ " '' . ., a~ ,Q
;" ~ 0~ 0~ 1 ~
', O O F~'~
,' V o ,rd - ~; h h h ~
~ P ~o m ~cl C) o ~ ~rl h "~ ~) ~ P ~ g ~
.. ~ o e~ :~ , o ~
. ! V rl ~ (D 1--I ~ O C'O ~ ' o ~ o h ~Q m a~
~ ~ o ~ ~ o o .'. ' . .
- 8 -- :.
Claims (6)
1. Process for the preparation of synthetic lubricating oils having a high viscosity index, very low pour point, low viscosity at 0°F, high thermal stability, high resistance to depolymerization, high flash point and very low carbon residue, characterized in that it comprises:
a) subjecting a polymer having a viscosity in the range of 250 to 15,000 cSt at 210°F and a boiling point higher than 175°C, obtained by polymerizing normal alpha-olefines having the general formula R-CH = CH2 wherein R is an alkyl radical containing from 2 to 16 carbon atoms, in the presence of a TiCl4/polyiminoalane cata-lyst and in an atmosphere of an inert gas and/or hydrogen having a hydrogen pressure of less than 1 kg/cm2, to a catalytic cracking carried out at atmospheric pressure and at a temperature of from 250 to 300°C, the volume of liquid per volume of catalyst per hour being comprised between 0.1 and 5, b) distilling the resulting product under vacuum up to a head temperature, referred to atmospheric pressure, of 400°C and c) subjecting the residue having a boiling point higher than 400°C to a catalytic hydrogenation.
a) subjecting a polymer having a viscosity in the range of 250 to 15,000 cSt at 210°F and a boiling point higher than 175°C, obtained by polymerizing normal alpha-olefines having the general formula R-CH = CH2 wherein R is an alkyl radical containing from 2 to 16 carbon atoms, in the presence of a TiCl4/polyiminoalane cata-lyst and in an atmosphere of an inert gas and/or hydrogen having a hydrogen pressure of less than 1 kg/cm2, to a catalytic cracking carried out at atmospheric pressure and at a temperature of from 250 to 300°C, the volume of liquid per volume of catalyst per hour being comprised between 0.1 and 5, b) distilling the resulting product under vacuum up to a head temperature, referred to atmospheric pressure, of 400°C and c) subjecting the residue having a boiling point higher than 400°C to a catalytic hydrogenation.
2. Process according to claim 1, wherein the volume of liquid per volume of catalyst per hour is comprised between 0.5 and 2.
3. Process according to claims 1 or 2, wherein the catalyst used in the cracking step contains oxides or sulphides of metals selected from groups IV to the VIII of the Periodical System and is supported on a carrier having a weak Lewis acidity.
4. Process according to claims 1 or 2, wherein the catalyst used in the cracking step contains oxides and sulphides of metals selected from groups VI to the VIII of the Periodical System and is supported on alumina.
5. Process according to claim 1, wherein the hydroge-nation is carried out in the presence of a catalyst containing 0.3%
of palladium on alumina, at a temperature of 200°C and under a hydrogen pressure of 100 kg/cm2, for a period of 5 hours.
of palladium on alumina, at a temperature of 200°C and under a hydrogen pressure of 100 kg/cm2, for a period of 5 hours.
6. Process according to claim 1, wherein the polymer subjected to catalytic cracking has a viscosity comprised between 660 and 1,150 cSt at 210°F.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21459/73A IT981302B (en) | 1973-03-12 | 1973-03-12 | SYNTHETIC LUBRICANT OILS FROM CATALYTIC CRACKING OF VERY HIGH VISCOSITY POLYMERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1036586A true CA1036586A (en) | 1978-08-15 |
Family
ID=11182096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA194,659A Expired CA1036586A (en) | 1973-03-12 | 1974-03-12 | Synthetic lubricating oils from catalytic cracking of polymers of a very high viscosity |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5338117B2 (en) |
| CA (1) | CA1036586A (en) |
| CH (1) | CH615456A5 (en) |
| CS (1) | CS208698B2 (en) |
| DD (1) | DD110304A5 (en) |
| DK (1) | DK143071C (en) |
| IT (1) | IT981302B (en) |
| NO (1) | NO140138C (en) |
| PL (1) | PL88821B1 (en) |
| SE (1) | SE385224B (en) |
| SU (1) | SU650495A3 (en) |
| YU (1) | YU35783B (en) |
| ZA (1) | ZA741592B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54170615U (en) * | 1978-05-22 | 1979-12-03 | ||
| JPS5789607U (en) * | 1980-11-14 | 1982-06-02 | ||
| US6050631A (en) * | 1994-08-25 | 2000-04-18 | Mitsubishi Jidosha Kogyo Kabushiki Kaisha | Impact energy absorbing structure for vehicle cabin |
-
1973
- 1973-03-12 IT IT21459/73A patent/IT981302B/en active
-
1974
- 1974-03-05 CH CH306974A patent/CH615456A5/en not_active IP Right Cessation
- 1974-03-11 YU YU653/74A patent/YU35783B/en unknown
- 1974-03-11 NO NO740844A patent/NO140138C/en unknown
- 1974-03-11 SU SU742007414A patent/SU650495A3/en active
- 1974-03-11 DK DK132274A patent/DK143071C/en not_active IP Right Cessation
- 1974-03-12 PL PL1974169447A patent/PL88821B1/en unknown
- 1974-03-12 DD DD177139A patent/DD110304A5/xx unknown
- 1974-03-12 CS CS741796A patent/CS208698B2/en unknown
- 1974-03-12 CA CA194,659A patent/CA1036586A/en not_active Expired
- 1974-03-12 JP JP2778774A patent/JPS5338117B2/ja not_active Expired
- 1974-03-12 SE SE7403319A patent/SE385224B/en unknown
- 1974-03-12 ZA ZA00741592A patent/ZA741592B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO140138C (en) | 1979-07-11 |
| YU35783B (en) | 1981-06-30 |
| NO140138B (en) | 1979-04-02 |
| DK143071C (en) | 1981-11-02 |
| JPS5338117B2 (en) | 1978-10-13 |
| NO740844L (en) | 1974-09-13 |
| YU65374A (en) | 1980-10-31 |
| IT981302B (en) | 1974-10-10 |
| PL88821B1 (en) | 1976-09-30 |
| SU650495A3 (en) | 1979-02-28 |
| DD110304A5 (en) | 1974-12-12 |
| DK143071B (en) | 1981-03-23 |
| SE385224B (en) | 1976-06-14 |
| CS208698B2 (en) | 1981-09-15 |
| CH615456A5 (en) | 1980-01-31 |
| JPS5025690A (en) | 1975-03-18 |
| ZA741592B (en) | 1975-02-26 |
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