NO140192B - PROCEDURE FOR THE PRODUCTION OF SYNTHETIC LUBRICATION OIL BY POLYMERIZATION OF ALFA OLEFINES, HYDROCRACKING AND VACUUM DISTILLATION - Google Patents
PROCEDURE FOR THE PRODUCTION OF SYNTHETIC LUBRICATION OIL BY POLYMERIZATION OF ALFA OLEFINES, HYDROCRACKING AND VACUUM DISTILLATION Download PDFInfo
- Publication number
- NO140192B NO140192B NO740843A NO740843A NO140192B NO 140192 B NO140192 B NO 140192B NO 740843 A NO740843 A NO 740843A NO 740843 A NO740843 A NO 740843A NO 140192 B NO140192 B NO 140192B
- Authority
- NO
- Norway
- Prior art keywords
- viscosity
- catalyst
- polymerization
- hydrogen
- hydrocracking
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 15
- 238000006116 polymerization reaction Methods 0.000 title claims description 7
- 239000010689 synthetic lubricating oil Substances 0.000 title claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000005292 vacuum distillation Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000009835 boiling Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 22
- 238000004523 catalytic cracking Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
Classifications
-
- 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
- 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
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/10—Chemical modification of a polymer including a reactive processing step which leads, inter alia, to morphological and/or rheological modifications, e.g. visbreaking
-
- 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)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av syntetisk smøreolje med høy viskositetsindeks, The present invention relates to a method for the production of synthetic lubricating oil with a high viscosity index,
meget lavt hellepunkt, lav viskositet ved -18°C, høy termisk stabilitet, høy motstand overfor depolymerisering, høy flammepunkt og meget lav karbonrest, og det særegne ved fremgangs- very low pour point, low viscosity at -18°C, high thermal stability, high resistance to depolymerisation, high flash point and very low carbon residue, and the distinctive
måten i henhold til oppfinnelsen er at polymerene med meget høy kinematisk viskositet med kokepunkt høyere enn 17 5°C, oppnådd ved polymerisering ved ét manometrisk trykk på opptil 1 kg/cm<2 >under en atmosfære av inert gass og/eller hydrogen av normale a-olefiner med den generelle formel R - CH = CI^ hvori R er et alkylradikal inneholdende 2-16 karbonatomer, i nærvær av katalysatoren TiCl4/polyiminoalan, utsettes for en katalytisk hydrocracking ved temperatur på fra 300 til 400 C, under en atmosfære av hydrogen og eventuelt inert gass idet væskevolum pr. katalysatorvolum pr. time utgjør mellom 0,1 og 5, foretrukket mellom 0,25 og 1,5 idet hydrogentrykket er mellom 20 og 200 kg/cm 2 , fortrinnsvis mellom 20 og 100 kg/cm 2, det oppnådde produkt destilleres under vakuum for fraskilling av en ønsket fraksjon som har kokepunkt over 400°C ved atmosfæretrykk. the way according to the invention is that the polymers with very high kinematic viscosity with a boiling point higher than 17 5°C, obtained by polymerization at one manometric pressure of up to 1 kg/cm<2 >under an atmosphere of inert gas and/or hydrogen of normal α-olefins with the general formula R - CH = CI^ in which R is an alkyl radical containing 2-16 carbon atoms, in the presence of the catalyst TiCl4/polyiminoalane, are subjected to a catalytic hydrocracking at a temperature of from 300 to 400 C, under an atmosphere of hydrogen and possibly inert gas as the liquid volume per catalyst volume per hour is between 0.1 and 5, preferably between 0.25 and 1.5, the hydrogen pressure being between 20 and 200 kg/cm 2 , preferably between 20 and 100 kg/cm 2 , the product obtained is distilled under vacuum to separate a the desired fraction which has a boiling point above 400°C at atmospheric pressure.
Fremgangsmåten i henhold til oppfinnelsen består således hoved-sakelig av to påfølgende faser. The method according to the invention thus mainly consists of two successive phases.
Den første fase vedrører fremstilling av polymerer med en ganske høy molekylvekt med et bredt viskositetsområde omfattende fra 250 cSt opp til 15.000 cSt ved 99°C. Slike polymerer oppnås med høye utbytter ved polymerisering av normale a-olefinblandinger fra voks-cracking eller enkle normale a-olefiner med den generelle formel R - CH = CH2 hvori R er et alkylradikal inneholdende fra 2-16 karbonatomer, i nærvær av en katalysator dannet av kom-plekset TiCl4/PIA (titan-tetraklorid/polyiminoalan), ved å arbeide i en inert atmosfære, eller som minst delvis er erstattet med hydrogen og i alle fall med et manometrisk hydrogentrykk ikke høy-ere enn 1 kg/cm 2og deretter destillere produktet fra polymeriser-ingen opp til en topp-temperatur på 175°C. The first phase concerns the production of polymers with a fairly high molecular weight with a wide viscosity range comprising from 250 cSt up to 15,000 cSt at 99°C. Such polymers are obtained with high yields by polymerization of normal α-olefin mixtures from wax cracking or simple normal α-olefins of the general formula R - CH = CH2 in which R is an alkyl radical containing from 2-16 carbon atoms, in the presence of a catalyst formed of the complex TiCl4/PIA (titanium tetrachloride/polyiminoalane), by working in an inert atmosphere, or which is at least partially replaced with hydrogen and in any case with a manometric hydrogen pressure no higher than 1 kg/cm 2 and then distill the product from the polymerization up to a peak temperature of 175°C.
Den annen fase av fremgangsmåten i henhold til oppfinnelsen og The second phase of the method according to the invention and
som fører frem til de syntetiske smøreoljer, består i å under-kaste polymerene med høy viskositet med et kokepunkt høyere enn 175°C, oppnådd i den første fase, for en hydrogenerende katalytisk cracking, for å redusere molekylvekten av polymerene og oppnå oljer innenfor et viskositetsområde vanlig for smøreoljer. leading to the synthetic lubricating oils, consists in subjecting the high-viscosity polymers with a boiling point higher than 175°C, obtained in the first phase, to a hydrogenating catalytic cracking, in order to reduce the molecular weight of the polymers and obtain oils within a viscosity range common for lubricating oils.
Med denne behandling bestående i hydrogenerende katalytisk cracking av polymerene med høy viskositet oppnås smøreoljer med meget gode egenskaper og med spesielt forbedret termisk stabilitet. With this treatment consisting in hydrogenating catalytic cracking of the polymers with high viscosity, lubricating oils with very good properties and with particularly improved thermal stability are obtained.
Ved passende endring av katalysatortype og arbeidsbetingelsene, for den hydrogenerende cracking (temperatur, volumhastighet, hydrogentrykk) er det mulig å oppnå oljer med alle de ønskede viskositeter, fra 4 cSt opp til 20 - 30 - 50 cSt ved 99°C. By suitably changing the type of catalyst and the working conditions for the hydrogenating cracking (temperature, volume velocity, hydrogen pressure) it is possible to obtain oils with all the desired viscosities, from 4 cSt up to 20 - 30 - 50 cSt at 99°C.
Ved den hydrogenerende katalytiske cracking av polymerene med høy molekylvekt er det foretrukket å anvende katalysatorer med bærere som har en svak Lewis-surhet, av aluminiumoksydtypen, for å oppnå så stor dannelse av lavtkokende produkter som mulig. Selve katalysatoren består fordelaktig av oksyder eller sulfider av metallene fra gruppene VI til VIII i det periodiske system, f.eks. Co/Mo. Ved behandlingen, er de variable storrelser, med den samme anvendte katalysator, temperaturen, volumhastigheten og hydrogentrykket. In the hydrogenating catalytic cracking of the polymers with a high molecular weight, it is preferred to use catalysts with supports that have a weak Lewis acidity, of the alumina type, in order to achieve as much formation of low-boiling products as possible. The catalyst itself advantageously consists of oxides or sulphides of the metals from groups VI to VIII in the periodic table, e.g. Co/Mo. In the treatment, they are variable sizes, with the same used catalyst, the temperature, the volume rate and the hydrogen pressure.
De brukbare temperaturer er fra 300 - ^-00°C, volumhastigheten, LHSV, betegnet som v/v/h, nemlig •volum væske pr, volum katalysator pr. time, kan utgjore fra 0,1 til 5? foretrukket mellom 0,25 og 1,5. The usable temperatures are from 300 - ^-00°C, the volume velocity, LHSV, denoted as v/v/h, namely •volume of liquid per, volume of catalyst per. hour, can amount from 0.1 to 5? preferably between 0.25 and 1.5.
Hydrogentrykket varierer fortrinnsvis fra 50 opp til 100 kg/cm 2. The hydrogen pressure preferably varies from 50 up to 100 kg/cm 2 .
Den hydrogenerende katalytiske cracking ble gjennomfort ved å la polymeren med høy molekylvekt oppnådd i den første fase strømme under kontrollert hydrogentrykk gjennom en rorformet reaktor som var elektrisk oppvarmet og som inneholdt hydrogeneringskatalysatoren. The hydrogenating catalytic cracking was carried out by allowing the high molecular weight polymer obtained in the first phase to flow under controlled hydrogen pressure through a tubular reactor which was electrically heated and which contained the hydrogenation catalyst.
Det således oppnådde produkt fraksjoneres under redusert trykk opp til en topp-temperatur, ved atmosfæretrykk på U-00°C. Resten med et kokepunkt hoyere enn <l>f00°C utgjor den syntetiske smdre-olje med hoy kvalitet. The product thus obtained is fractionated under reduced pressure up to a peak temperature, at atmospheric pressure of U-00°C. The residue with a boiling point higher than <l>f00°C constitutes the high quality synthetic lubricant oil.
Denne olje, som kommer fra den hydrogenerende cracking , kan betraktes som mettet og behover ingen ytterligere hydrogenering. Alt etter viskositeten av tilforselspolymerene i det betraktede område fra 660 cSt opp til 5-330 cSt ved 99°C, vil utbyttet av olje med et kokepunkt hoyere enn <l>f00°G endres fra 66$ til 61 % hvis det onskes å oppnå oljer med en viskositet på 18 cSt ved 99°C og vil endre seg fra 77% til 7h% hvis det onskes en viskositet på omtrent 30 cSt ved 99 C. This oil, which comes from the hydrogenating cracking, can be considered saturated and needs no further hydrogenation. Depending on the viscosity of the feed polymers in the considered range from 660 cSt up to 5-330 cSt at 99°C, the yield of oil with a boiling point higher than <l>f00°G will change from 66$ to 61% if it is desired to obtain oils with a viscosity of 18 cSt at 99°C and will change from 77% to 7h% if a viscosity of approximately 30 cSt at 99°C is desired.
Oljen frembragt ved den foreliggende oppfinnelse har en viskositet på omtrent 18 cSt ved 99°C, har en viskositetsindeks på 132 beregnet etter ASTM Method D 2270/A og på 158 beregnet etter ASTM Method 2270/B, hellepunkt på -<>>+80C, meget lav karbonrest, og betraktelig motstand overfor depolymerisering, hoy termisk stabilitet og flampunkt på 2<*>+6°C. The oil produced by the present invention has a viscosity of approximately 18 cSt at 99°C, has a viscosity index of 132 calculated according to ASTM Method D 2270/A and of 158 calculated according to ASTM Method 2270/B, pour point of -<>>+80C , very low carbon residue, and considerable resistance to depolymerisation, high thermal stability and flash point of 2<*>+6°C.
Den folgende beskrivelse illustrerer oppfinnelsen. The following description illustrates the invention.
:I eksemplene med de kinematiske viskositet.er bestemt i henhold tii ASTM Method D Mf 5. For viskositetsindeksen ble det bestemt to verdier, den ene beregnet i henhold til ASTM Method D 2270/A og den annen beregnet etter ..ASTM Method D 2270/B, som er mer eksakt for viskositetsindekser hoyere enn 100. Hellepunktet ble bestemt i henhold til ASTM Method D 97. Jodtallet ble bestemt i henhold til IP 8*f. In the examples with the kinematic viscosities are determined according to ASTM Method D Mf 5. For the viscosity index, two values were determined, one calculated according to ASTM Method D 2270/A and the other calculated according to ..ASTM Method D 2270 /B, which is more accurate for viscosity indices higher than 100. The pour point was determined according to ASTM Method D 97. The iodine number was determined according to IP 8*f.
Eksempel 1 . Example 1.
o o
En polymer med et kokepunkt hoyere enn 175 C, oppnådd ved poly-merisasjon av Cg til C1Q a-olefiner fra voks-cracking og med en viskositet ved 99°C på 660 cSt bie underkastet hydrogenerende katalytisk cracking for å redusere viskositeten og oppnå smoreoljer. A polymer with a boiling point higher than 175 C, obtained by polymerization of Cg to C1Q α-olefins from wax cracking and with a viscosity at 99°C of 660 cSt was subjected to hydrogenating catalytic cracking to reduce viscosity and obtain lubricating oils.
Behandlingen ble gjennomfort ved å la polymeren stromme med styrt hastighet og under et hydrogentrykk på 50 - 100 kg/cm<p >gjennom en rorformet reaktor som var elektrisk oppvarmet og hadde en diameter på *f0 mm og inneholdt 150 cc hydrogenerings-katalysator basert på Co og Mo på aluminiumoksyd ca. 1 mm. Under provene var det en gass-resirkulasjon. Produktene oppnådd i de forskjellige prover ble destillert under vakuum opp til en topp-temperatur ved atmosfæretrykk på <1>+00°C. The treatment was carried out by allowing the polymer to flow at a controlled rate and under a hydrogen pressure of 50 - 100 kg/cm<p >through a tubular reactor which was electrically heated and had a diameter of *f0 mm and contained 150 cc of hydrogenation catalyst based on Co and Mo on aluminum oxide approx. 1 mm. During the test there was a gas recirculation. The products obtained in the different samples were distilled under vacuum up to a peak temperature at atmospheric pressure of <1>+00°C.
Resten med et kokepunkt hoyere enn <l>+00°C utgjorde den syntetiske smoreolje. The residue with a boiling point higher than <l>+00°C constituted the synthetic lubricating oil.
De forholdsvise resultater er vist i den folgende tabell.I. The relative results are shown in the following table.I.
Ved å undersoke disse resultater var det mulig å slutte at de viktigste variabler var temperaturen og volumhastigheten, mens hydrogentrykket hadde en ikke merkbar innvirkning. I virkelig-heten forte en variasjon av trykket fra 50 opp til 100 kg/cm , med de andre variabler stabile, ikke til noen særlig endring av resultatene. By examining these results it was possible to conclude that the most important variables were the temperature and the volume velocity, while the hydrogen pressure had an unnoticeable impact. In reality, a variation of the pressure from 50 up to 100 kg/cm, with the other variables stable, did not lead to any particular change in the results.
Fra en grafisk fremstilling ble det sluttet at hydrogenerte" oljer med et kokepunkt hoyere enn lf00°C og med en viskositet ved 99°C på omtrent 18 cSt kunne oppnås ved å arbeide med en volumhastighet på 0,25 ved temperatur på omtrent 375°C eller med en volumhastighet på 0,5 ved en temperatur på omtrent 385°C eller med en volumhastighet på 1,5 ved temperatur på omtrent kOO°C. From a graphical representation it was concluded that "hydrogenated" oils with a boiling point higher than 100°C and with a viscosity at 99°C of about 18 cSt could be obtained by operating at a volume rate of 0.25 at a temperature of about 375°C or at a volume rate of 0.5 at a temperature of about 385°C or at a volume rate of 1.5 at a temperature of about kOO°C.
Utbyttene av oljer med denne viskositet var omtrent like og utgjorde omtrent 65 - 66 vekt%. Viskositetsindeksene var hoye og hellepunktene meget lave. The yields of oils with this viscosity were about the same and amounted to about 65 - 66% by weight. The viscosity indices were high and the pour points very low.
På grunn av jod-tallene kunne de oppnådde oljer betraktes som mettet. Due to the iodine numbers, the oils obtained could be considered saturated.
Eksempel 2 Example 2
Polymeren med et kokepunkt hoyere enn 175<C>>C anvendt i eksempel 1 og med en viskositet ved 99°C på 660 cSt ble utsatt for en hydrogenerende katalytisk cracking ved i det samme apparat som i eksempel 1 å anvende 150 cc katalysator basert på oksyder av kobolt og molybden på en bærer som besto av 25% silisiumoksyd og 75$ ca. 1,5 mm aluminiumoksyd. Gass-resirkulasjonen var 735 1/1. The polymer with a boiling point higher than 175<C>>C used in example 1 and with a viscosity at 99°C of 660 cSt was subjected to a hydrogenating catalytic cracking by using, in the same apparatus as in example 1, 150 cc of catalyst based on oxides of cobalt and molybdenum on a carrier which consisted of 25% silicon oxide and 75$ approx. 1.5 mm aluminum oxide. The gas recirculation was 735 1/1.
Resultatene av provene er gjengitt i tabell II. The results of the test are reproduced in table II.
Ved å sammenligne disse resultater med resultatene fra eksempel 1 ble det bemerket at med samme viskositet, var utbyttet av oljer med et kokepunkt hoyere enn <l>fOO°C lavere når det ble anvendt en katalysator med en bærer med storre surhet og de nod-vendige temperaturer var lavere. By comparing these results with those of Example 1, it was noted that with the same viscosity, the yield of oils with a boiling point higher than <l>fOO°C was lower when a catalyst with a support of greater acidity was used and the nod- turning temperatures were lower.
Fra en grafisk fremstilling ble det bestemt at oljer med en viskositet på omtrent 18 cSt ved 99°C ble oppnådd med den nevn-te katalysator ved å arbeide med en volumhastighet på 0,5 ved en temperatur på omtrent 355°C eller med en volumhastighet på 1.5 ved temperatur på omtrent 365°C. From a graphical representation, it was determined that oils having a viscosity of about 18 cSt at 99°C were obtained with said catalyst by operating at a volume rate of 0.5 at a temperature of about 355°C or at a volume rate of 1.5 at a temperature of approximately 365°C.
Utbyttene var i begge tilfeller omtrent 60%. Viskositetsindeksene forble hoye, og hellepunktene meget lave. The yields in both cases were approximately 60%. The viscosity indices remained high, and the pour points very low.
Eksempel 3. Example 3.
Den hydrogenerende katalytiske cracking ble gjennomfort ved som tilforsel å anvende en polymer med et kokepunkt hoyere enn 175 C oppnådd ved polymerisering av a-olefiner Cg*- C^ q fra voks-cracking og med en viskositet på 5-330 cSt ved 99°C. The hydrogenating catalytic cracking was carried out by using as feed a polymer with a boiling point higher than 175 C obtained by polymerization of α-olefins Cg*- C^ q from wax cracking and with a viscosity of 5-330 cSt at 99°C .
Ka tal yr-;,-i L.; r'.mi var den samme som anvendt i eksempel 1 og utgjorde noyaktig 150 cc basert på oksyder av kobolt og molybden på aluminiumoksyd. Ka tal yr-;,-i L.; r'.mi was the same as used in example 1 and amounted to exactly 150 cc based on oxides of cobalt and molybdenum on aluminum oxide.
Gass-resirkuleringen var på 735 1/1. The gas recycling was 735 1/1.
Apparatet var det samme som apparatet anvendt i eksempel 1. The apparatus was the same as the apparatus used in example 1.
Resultatene av de gjennomforte prover er gjengitt i tabell III. The results of the tests carried out are reproduced in table III.
Ved å sammenligne disse resultater med resultatene fra eksempel 1, hvor forsøkene ble gjennomfort med samme katalysator på aluminiumoksyd, ble det bemerket at ved som tilforsel å anvende en polymer med hoyere viskositet, var det for opp-nåelse av oljer med samme viskositeter nodvendig å arbeide ved en hoyere temperatur og med lavere utbytte som resultat. By comparing these results with the results from example 1, where the experiments were carried out with the same catalyst on aluminum oxide, it was noted that by using a polymer with a higher viscosity as feed, it was necessary to work to obtain oils with the same viscosities at a higher temperature and with a lower yield as a result.
Eksempel h . Example h.
Den syntetiske olje oppnådd ved forsok 11 i eksempel 1 (se tabell I) ble valgt som representativ for fremgangsmåten i henhold til oppfinnelsen. Ved at den kom fra en hydrogenerende behandling, var den fullstendig mettet, som dette kunne bestemmes ved hjelp av jod-tallet. The synthetic oil obtained in trial 11 in example 1 (see Table I) was chosen as representative of the method according to the invention. As it came from a hydrogenating treatment, it was completely saturated, as this could be determined by means of the iodine number.
De andre egenskaper for en slik olje er gjengitt i tabell IV. The other properties of such an oil are reproduced in table IV.
Fra verdiene for viskositeten ved 99° C og ved -18°C, ved From the values for the viscosity at 99° C and at -18° C, at
siden av verdiene for hellepunktet, kan det sluttes at oljen har gode egenskaper både ved hoye og lave temperaturer. aside from the values for the pour point, it can be concluded that the oil has good properties both at high and low temperatures.
Videre skal det bemerkes at oljen har en meget lav verdi for karbonrest og et meget hoyt flampunkt. Furthermore, it should be noted that the oil has a very low value for carbon residue and a very high flash point.
Eksempel 5. Example 5.
Oljen med kokeområde på lf00oC+ (som koker ved en temperatur hoyere enn k- 00°C) oppnådd i forsok 11 i eksempel 1, ble utsatt for prove på skjær-stabilitet med en sonisk oscillator VRaytheon" i 15 minutter ved en temperatur på 38°C (ASTM D 2603-70). Resultatene er gjengitt i den folgende tabell V. The oil with a boiling range of lf00oC+ (boiling at a temperature higher than k- 00°C) obtained in trial 11 of Example 1 was subjected to a shear stability test with a sonic oscillator VRaytheon" for 15 minutes at a temperature of 38° C (ASTM D 2603-70). The results are reproduced in the following table V.
Fra disse resultatene var det mulig å utlede at oljen som ble oppnådd ved fremgangsmåten i henhold til oppfinnelsen, var motstandsdyktig ved den soniske de-polymeriseringsprdve. From these results it was possible to deduce that the oil obtained by the method according to the invention was resistant to the sonic depolymerization process.
Eksempel 6. Example 6.
Den <1>fOO°C+ olje som var oppnådd ved forsok 11 i eksempel 1 ble utsatt for den termiske stabilitetsprove i henhold til P'ederal Standard Method No. 2508 " Thermal Stability of Lubricating The <1>fOO°C+ oil obtained in Trial 11 of Example 1 was subjected to the thermal stability test according to Federal Standard Method No. 2508 “ Thermal Stability of Lubricating
and Hydraulic Fluids", som besto i å holde 20 cc av oljen ved en temperatur på 260°C i 2h timer under undersøkelse i et glass-ror som var forseglet med flamme, idet oljen forst var underkastet en avgassing. and Hydraulic Fluids", which consisted of keeping 20 cc of the oil at a temperature of 260°C for 2 hours under examination in a glass tube that was sealed with a flame, the oil having first been subjected to degassing.
Resultatene av provene er gjengitt i tabell VI. The results of the test are reproduced in table VI.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21458/73A IT981301B (en) | 1973-03-12 | 1973-03-12 | SYNTHETIC LUBRICANT OILS FROM HYDROGENATING CATALYTIC CRACKING OF POLYMERS WITH VERY HIGH VISCO SITA |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO740843L NO740843L (en) | 1974-09-13 |
| NO140192B true NO140192B (en) | 1979-04-09 |
| NO140192C NO140192C (en) | 1979-07-18 |
Family
ID=11182077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO740843A NO140192C (en) | 1973-03-12 | 1974-03-11 | PROCEDURE FOR THE PRODUCTION OF SYNTHETIC LUBRICATION OIL BY POLYMERIZATION OF ALFA OLEFINES, HYDROCRACKING AND VACUUM DISTILLATION |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5338116B2 (en) |
| BE (1) | BE812157A (en) |
| CA (1) | CA1036587A (en) |
| CH (1) | CH617225A5 (en) |
| CS (1) | CS208697B2 (en) |
| DD (1) | DD110515A5 (en) |
| DK (1) | DK143505C (en) |
| FR (1) | FR2221514B1 (en) |
| GB (1) | GB1461134A (en) |
| IT (1) | IT981301B (en) |
| NL (1) | NL155843B (en) |
| NO (1) | NO140192C (en) |
| PL (1) | PL88682B1 (en) |
| SE (1) | SE385223B (en) |
| SU (1) | SU674665A3 (en) |
| YU (1) | YU35784B (en) |
| ZA (1) | ZA741593B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0533391A (en) * | 1991-03-22 | 1993-02-09 | Kajima Corp | Post-girder joining section structure |
-
1973
- 1973-03-12 IT IT21458/73A patent/IT981301B/en active
-
1974
- 1974-03-05 CH CH306874A patent/CH617225A5/en not_active IP Right Cessation
- 1974-03-11 DK DK132374A patent/DK143505C/en not_active IP Right Cessation
- 1974-03-11 SU SU742007972A patent/SU674665A3/en active
- 1974-03-11 YU YU654/74A patent/YU35784B/en unknown
- 1974-03-11 BE BE141894A patent/BE812157A/en not_active IP Right Cessation
- 1974-03-11 GB GB1083474A patent/GB1461134A/en not_active Expired
- 1974-03-11 NO NO740843A patent/NO140192C/en unknown
- 1974-03-11 FR FR7408208A patent/FR2221514B1/fr not_active Expired
- 1974-03-12 NL NL7403336.A patent/NL155843B/en not_active IP Right Cessation
- 1974-03-12 PL PL1974169449A patent/PL88682B1/pl unknown
- 1974-03-12 CS CS741795A patent/CS208697B2/en unknown
- 1974-03-12 CA CA194,794A patent/CA1036587A/en not_active Expired
- 1974-03-12 DD DD177148A patent/DD110515A5/xx unknown
- 1974-03-12 ZA ZA00741593A patent/ZA741593B/en unknown
- 1974-03-12 JP JP2778674A patent/JPS5338116B2/ja not_active Expired
- 1974-03-12 SE SE7403318A patent/SE385223B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL88682B1 (en) | 1976-09-30 |
| CA1036587A (en) | 1978-08-15 |
| YU35784B (en) | 1981-06-30 |
| FR2221514B1 (en) | 1978-12-01 |
| YU65474A (en) | 1980-10-31 |
| GB1461134A (en) | 1977-01-13 |
| SE385223B (en) | 1976-06-14 |
| NL7403336A (en) | 1974-09-16 |
| NL155843B (en) | 1978-02-15 |
| CH617225A5 (en) | 1980-05-14 |
| NO740843L (en) | 1974-09-13 |
| DE2411562B2 (en) | 1977-04-21 |
| AU6657474A (en) | 1975-09-18 |
| FR2221514A1 (en) | 1974-10-11 |
| DD110515A5 (en) | 1974-12-20 |
| NO140192C (en) | 1979-07-18 |
| ZA741593B (en) | 1975-02-26 |
| JPS5025689A (en) | 1975-03-18 |
| DK143505B (en) | 1981-08-31 |
| DE2411562A1 (en) | 1974-09-26 |
| DK143505C (en) | 1982-01-04 |
| IT981301B (en) | 1974-10-10 |
| CS208697B2 (en) | 1981-09-15 |
| BE812157A (en) | 1974-07-01 |
| SU674665A3 (en) | 1979-07-15 |
| JPS5338116B2 (en) | 1978-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3883417A (en) | Two-stage synthesis of lubricating oil | |
| US5208403A (en) | High VI lubricant blends from slack wax | |
| DE69315274T2 (en) | Manufacture of lubricating oils | |
| US4078010A (en) | Hydrogenated olefine oligomers | |
| FI95925B (en) | Lubricant mixtures with high viscosity indices | |
| US3957898A (en) | Synthetic lubricating oils from thermal cracking or polymers having very high viscosity | |
| EP0046634A2 (en) | Process for production of hydrogenated hydrocarbon polymers and catalyst useful therefore | |
| US3923919A (en) | Ethylene-propylene copolymer oil | |
| US2700661A (en) | Halocarbon polymers | |
| NO140192B (en) | PROCEDURE FOR THE PRODUCTION OF SYNTHETIC LUBRICATION OIL BY POLYMERIZATION OF ALFA OLEFINES, HYDROCRACKING AND VACUUM DISTILLATION | |
| US5817899A (en) | Polyalphaolefin dimers having low kinematic viscosities | |
| US5420373A (en) | Controlled formation of olefin oligomers | |
| US3737477A (en) | Process of preparing ethylene propylene copolymer oils | |
| US2436069A (en) | Oils and greases obtained by pyrolysis of tetrafluoroethyleneolefin copolymers | |
| JPS6143400B2 (en) | ||
| US3884988A (en) | Production of synthetic lubricants from alpha-olefins through a ternary catalytic system | |
| US4138227A (en) | Production of low pour, low sulfur fuel oils | |
| NO140138B (en) | PROCEDURE FOR THE PREPARATION OF SYNTHETIC LUBRICATION OILS BY POLYMERIZATION OF ALFA OLEFINES, CATALYTIC CRACKING, VACUUM DISTILLATION AND HYDROGENATION | |
| US2211944A (en) | Treatment of lubricating oils | |
| US5550307A (en) | Increased dimer yield of olefin oligomers through catalyst modifications | |
| US2197768A (en) | Polymerized hydrocarbon composition | |
| CA1036585A (en) | Synthetic lubricating oils from thermal cracking of polymers having very high viscosity | |
| EP0323759A2 (en) | Olefin polymerization process with product viscosity and pour point control | |
| US3929923A (en) | Process for preparation of isomers of 1-cyclohexyl-1,3,3-trimethylhydrindane | |
| US2197769A (en) | Lubricant and process of making the same |