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RS50382B - Izoparafinska osnovna smeša za podmazivanje - Google Patents

Izoparafinska osnovna smeša za podmazivanje

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Publication number
RS50382B
RS50382B YUP-222/00A YU22200A RS50382B RS 50382 B RS50382 B RS 50382B YU 22200 A YU22200 A YU 22200A RS 50382 B RS50382 B RS 50382B
Authority
RS
Serbia
Prior art keywords
mixture
lubricating oil
measured
liquid hydrocarbon
base
Prior art date
Application number
YUP-222/00A
Other languages
English (en)
Inventor
Thomas FORBUS
Zhaozhong JIANG
Radndall PARTRIDGE
Suzanne SCHRAMM
Jeffrey TREWELLA
Original Assignee
Mobil Oil Corporation,
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation, filed Critical Mobil Oil Corporation,
Publication of YU22200A publication Critical patent/YU22200A/sh
Publication of RS50382B publication Critical patent/RS50382B/sr

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    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • C10M2203/06—Well-defined aromatic compounds
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Tečna ugljovodonična smeša, naznačena time, što obuhvata parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je: BI - 0,5 (CH2>4) > 15, i BI + 0,85 (CH2>4)< 45, mereno prekopomenute tečne ugljovodonične smeše kao celine.Prijava sadrži još 20 patentnih zahteva.

Description

Ova prijava zahteva prioritet pod 35 USC §119 prema US privremenoj prijavi br. 60/062.824.
Razvijene su osnovne sirovine ulja za podmazivanje sa visokim učinkom koje imaju jedinstvene karakteristike sastava i koje pokazuju superiorne niskotemperaturne osobine u pogledu učinka.
Premijske osnovne sirovine ulja za podmazivanje sa visokim učinkom generalno pokazuju korisne viskoznosti u širokom opsegu temperatura, imaju poboljšan indeks viskoznosti i pokazuju mazivost, termičku i oksidativnu stabilnost i tačku mržnjenja jednaku ili bolju od uobičajenih mineralnih ulja. Takve pogodne reološke i osobine u pogledu učinka obogaćuju njihov učinak u formulacijama maziva u odnosu na formulacije na bazi mineralnih ulja, uključujući širi prozor operativne temperature. Međutim, premijske osnovne sirovine ulja za podmazivanje su skuplje za proizvodnju od uobičajenih maziva sa mineralnim uljima.
Mnogi istraživači su ispitivali načine pretvaranja relativno malo vrednih ugljovodoničnih sirovina, kao što je prirodni gas, u vrednije produkte, kao što su goriva i maziva. Pored toga, mnogo istraživanja je izvršeno u cilju katalitičkog poboljšanja parafinskih ugljovodoničnih sirovina, koje imaju znatne koncentracije pravolančanih parafinskih komponenata, pretvaranjem u korisnije produkte primenom hidroizomerizacije i deparafiniziranja, postupaka koji izomerizuju odnosno krekuju pravolančane parafinske voštane komponente ove sirovine.
Postupci za proizvodnju ugljovodoničnih goriva i maziva iz sinteznog gasa, smeše vodonika i ugljenmonoksida, poznati su već neko vreme, i od njih je verovatno najpoznatiji Fišer-Tropšov postupak. Procena razvoja ovog postupka i njegove značajnije karakteristike su dati u Kirk-Othmer-ovojEncyclopedia of Chemical Technologyrtreće izdanje, John Wiley & Sons, New York, 1980, vol. 11, str. 473-478.
U Fišer-Tropšovom postupku se sintezni gas, generalno formiran parcijalnom oksidacijom metana, provodi iznad katalizatora na povišenoj temperaturi i povišenom pritisku tako da se proizvodi više proizvoda redukcije ugljenmonoksida uključujući ugljovodonike, alkohole, masne kiseline i druga oksigenovana jedinjenja. U pogodnim okolnostima oksigenovani materijali mogu obuhvatati manje od 1 % od ukupnog željenog tečnog produkta. Ugljovodonični produkt je po prirodi visoko parafinski i tipično uključuje ugljovodonični gas, lake olefine, benzin, laka i teška goriva ulja (ulja za loženje i mazut) i parafinska (voštana) gasna ulja. Zbog toga što su visokoključajuće frakcije u ovom produktu uopšte isuviše voštane za generalnu primenu kao tečna goriva ili maziva, obično su potrebni dalja obrada ili poboljšanje pre nego što se mogu koristiti, kao takva ili dodata opštem rezervoaru proizvoda. Pogodno Fišer-Tropšovi produkti sadrže malo, ako uopšte i sadrže, tipičnih petrolejskih kontaminanata, kao što su aromatična jedinjenja, cikloparafinska jedinjenja (nafteni), sumporna jedinjenja i azotna jedinjenja, što je prouzrokovano relativno čistom prirodom sirovina: vodonika i ugljenmonoksida, i najzad metana ili prirodnog gasa.
SAD patent br. 4.500.417 otkriva konverziju visoko-ključajuće frakcije Fišer-Tropšovih produkata pomoću kontakta sa zeolitom visokog sadržaja silicijumdioksida i sa velikim porama i hidrogenizacionom komponentom tako da se proizvede frakcija destilata i frakcija ulja za podmazivanje okarakterisana visokim indeksom viskoznosti (VI) i niskom tačkom mrženjenja. Katalizatori uključuju zeolit Y, zeolit-beta, mordenit, ZSM-3, ZSM-4, ZSM-18 i ZSM-20.
SAD patent br. 4.906.350 otkriva postupak za dobivanje osnovnog ulja za ulje za podmazivanje sa visokim indeksom viskoznosti i niskom tačkom mrženja katalitičkim deparafiniziranjem najmanje dela hidrokrekovanih proizvoda frakcije mineralnog ulja koje sadrži parafin (vosak) iznad zeolitnog katalizatora odabranog između ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, ofretita, ferierita, zeolita-beta, zeolita-teta, zeolita-alfa i njihovih smeša.
SAD patent br. 4.943.672 otkriva postupak za hidroizomerizovanje Fišer-Tropšovog parafina (voska) tako da se proizvede ulje za podmazivanje koje ima visok indeks viskoznosti i nisku tačku mrženjenja prvo hidrotretiranjem parafina pod relativno oštrim uslovima i potom hidroizomerizovanjem hidrotretiranog parafina u prisustvu vodonika na naročitom katalizatoru: fluoridiranom metalu VIII grupe na aluminijumoksidu.
SAD patent br. 5.059.299 otkriva postupak za izomerizovanje presovanog parafina koji je dobiven iz mineralnih ulja i voska tako da se formiraju osnovne sirovine ulja za podmazivanje sa visokim indeksom viskoznosti i vrlo niskom tačkom mržnjenja izomerizovanjem iznad katalizatora koji sadrže element VI-VIII grupe na halogenovanom refraktornom metalnom oksidu kao nosaču, čemu sledi deparafiniziranje pomoću rastvarača.
SAD patenti br. 5.135.638 i 5.246.566 otkrivaju postupke izomerizacije parafina za proizvodnju ulja za podmazivanje koje ima odličnu viskoznost (VI) i nisku tačku mržnjenja izomerizovanjem parafinske petrolejske sirovine iznad molekulskih sita koja imaju izvesne dimenzije pora i najmanje jednog metala VIII grupe. Katalizatori uključuju SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 i-ZSM-35.
SAD patent br. 5.282.958 otkriva postupak za deparafiniziranje ugljovodonične sirovine koja uključuje pravolančane i malo razgranate parafine koji imaju 10 ili više atoma ugljenika da se proizvede deparafinizirano (odvošteno) ulje za podmazivanje koji koristi katalizatore specificirane geometrije pora i koji sadrže najmanje jedan metal VIII grupe. Osnovna sirovina se kontaktira sa katalizatorom u prisustvu vodonika; primeri katalizatora uključuju SSZ-32., ZSM-22 i ZSM-23.
SAD patent br. 5.306.860 otkriva postupak hidroizomerizovanja parafina, koji potiču iz Fišer-
Tropšovog postupka, iznad niza katalizatora, uključujući katalizator zeolit Y tako da se formiraju ulja za podmazivanje sa visokim indeksom viskoznosti (VI) i niskom tačkom mržnjenja.
SAD patent br. 5.362.378 otkriva konverziju Fišer-Tropšovih teških finalnih produkata sa katalizatorom platina/bor-zeolit-beta koji ima nisku alfa-aktivnost tako da se proizvede ulje za podmazivanje sa ekstra visokim indeksom viskoznosti (VI), koje se zatim može deparafinizirati uz primenu uobičajenog deparafiniziranja pomoću rastvarača ili povećanjem oštrine stupnja hidroizomerizacije.
Evropski patent br. 0 77 6 959 A2 otkriva postupak za dobivanje baznih ulja za podmazivanje koja imaju indeks viskoznosti od najmanje 150 iz Fišer-Tropšove parafinske (voštane) sirovine prvo hidroizomerizovanjem iznad pogodnog katalizatora u prisustvu vodonika a zatim deparafiniziranjem pomoću rastvarača ili katalitičkim deparafiniziranjem intermedijerne frakcije 390°C+.
Međutim, nijedna od gore diskutovanih referenci ne otkriva ili sugeriše dobivanje tečnih ugljovodonika specifičnog i ograničenog opsega smeša koje imaju naročitu kombinaciju osobina grananja, koja vodi do visoko poželjnih osobina podmazivanja uključujući neočekivanu kombinaciju visokog indeksa viskoznosti i niske tačke mržnjenja. U stvari, nijedna od citiranih referenci čak i ne otkriva ili sugeriše merenje indeksa grananja (BI) ili blizine grananja, kao što je to dole diskutovano.
SAD patent br. 4.827.064 otkriva sintetičke smeše za podmazivanje sa visokim indeksom viskoznosti koje sadrže polialfaolefine u kojima je meren »odnos grananja«, CH3</>CH2.
Otkrića gore opisanih SAD patenata su u njihovoj potpunosti ovde inkorporirana referencom.
Prvi predmet ovog pronalaska je proizvodnja jedinstvene tečne ugljovodonične smeše koja se može koristiti kao osnovna sirovina ulja za podmazivanje koja ima korisne niskotemperaturne viskozimetrijske osobine.
Drugi predmet ovog pronalaska je da obezbedi tržište za prirodni gas male vrednosti njegovim pretvaranjem u osnovne sirovine ulja za podmazivanje premijske vrednosti uz primenu kombinacije stupnjeva Fišer-Tropšove sinteze, hidroizomerizacije i katalitičkog deparafiniziranja.
Jedno oličenje ovog pronalaska se odnosi na smešu tečnih ugljovodonika koja ima parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja (ili "blizina grananja"), merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je:
mereno preko tečne ugljovodonične smeše kao celine.
Drugo oličenje ovog pronalaska se odnosi na smešu osnovne sirovine ulja za podmazivanje koja ima parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je:
raereno preko smeše osnovne sirovine ulja za podmazivanje kao celine.
U drugom oličenju, ovaj pronalazak se odnosi na smešu ulja za podmazivanje koja obuhvata smešu tečnih ugljovodonika koja ima parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je:
mereno preko tečne ugljovodonične smeše kao celine, i opciono, efektivne količine aditiva ulja za podmazivanje, kao što su, ali nisu ograničeni samo na njih, antioksidansi, aditivi protiv habanja, aditivi za ekstremne pritiske, modifikatori frikcije (trenja), poboljšivači indeksa viskoznosti, depresanti tačke mržnjenja, deterdženti, disperzanti, inhibitori korozije,
deaktivatori metala, aditivi za kompatibilnost zaptivanja, demulgatori, aditivi protiv penušanja i njihove smeše.
Gore navedeni i drugi predmeti, oličenja i prednosti ovog pronalaska bolje će se razumeti iz sledećih detaljnih opisa, uzetih u vezi sa priključenim crtežima, pri čemu su svi oni dati samo kao ilustracija i ni u kojem slučaju ne ograničavaju opseg ovog pronalaska.
Slika 1 je dijagram koji poredi niskotemperaturske viskozometrijske osobine tečnih ugljovodoničnih smeša datih ovim pronalaskom sa tipičnim hidroprerađenim osnovnim sirovinama ulja za podmazivanje.
Slika 2 je dijagram koji matematički ilustruje strukturna ograničenja BI i CH2>4, kao što su ovi dati u formulama (a) i (b), koje definišu granice ovde otkrivenih inventivnih smeša.
Slika 3 je grafičko poređenje dinamičkih viskoznosti (DV@-40°C) merenih CCS metodom ASTM D5392 i kinematičkih viskoznosti (KV@100°C) različitih ugljovodoničnih fluida uključujući i one koji su dati ovim pronalaskom.
Dalji opseg primenljivosti ovog pronalaska biće očigledan iz dole datog detaljnog opisa. Međutim, treba razumeti da su detaljan opis i specifični primeri, iako ukazuju na pogodna oličenja ovog pronalaska, dati samo ilustracijom, jer će iz ovog detaljnog opisa stručnjaku verziranom u ovoj oblasti biti očigledni različite izmene i modifikacije u duhu i opsegu ovog pronalaska.
Jedno oličenje ovog pronalaska se odnosi na tečnu ugljovodoničnu smešu parafinskih ugljovodoničnih komponenata u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je:
mereno preko tečne ugljovodonične smeše kao celine.
Ugljovodonični fluidi dati ovim pronalaskom pogodno imaju BI veći ili jednak 25,4 i blizine grananja (CH2>4) manje ili jednake 22,5 iako se bilo koja smeša koja zadovoljava ograničenja iz formula (a) i (b) nalazi u opsegu ovog pronalaska.
Merenje karakteristika grananja tečnih ugljovodonika datih ovim pronalaskom izvršeno je pomoću analize nuklearnom magnetnom rezonancijom (NMR) i dole će biti detaljnije opisano.
Tečna ugljovodonična smeša data ovim pronalaskom može imati vrlo niske koncentracije tipičnih zagadijivih kontaminanata koji su nađeni u osnovnim sirovinama ulja za podmazivanje prečišćenim iz prirodnih mineralnih ulja, već u zavisnosti od prirode sirovine koja je upotrebljena za proizvodnju tečnih ugljovodonika. Tipično, tečne ugljovodonične smeše date ovim pronalaskom imaju manje od 0,1 tež. % aromatičnih ugljovodonika, manje od 20 tež. ppm jedinjenja koja sadrže azot, manje od 20 tež. ppm jedinjenja koja sadrže sumpor i niske koncentracije naftenskih ugljovodonika, tj. cikloparafina. Očekuje se da koncentracije ovih kontaminanata mogu biti mnogo niže ili da mogu biti potpuno odsutne u inventivnim tečnim ugljovodonicima. Prema tome, nivoi koncentracija sumpornih i azotnih jedinjenja u inventivnim ugljovodoničnim smešama, kada potiču od Fišer-Tropšovih parafina su pogodno manji od 10 ppm (svaki) i još pogodnije manji od 1 ppm (svaki).
Niske koncentracije jedinjenja koja sadrže sumpor i jedinjenja koja sadrže azot su prvenstveno posledica prirode sirovine. Primena Fišer-Tropšovih parafina, formiranih od relativno čistih smeša sinteznog gasa, koje imaju malo, ako uopšte i imaju, jedinjenja koja sadrže azot ili sumpor, u gasnoj fazi rezultuje u ugljovodoničnim fluidima koji imaju vrlo niske koncentracije tipičnih kontaminanata. Nasuprot tome, mineralna ulja koja se nalaze u prirodi imaju znatne koncentracije organskih sumpornih i azotnih jedinjenja koja se teško ili nikako ne mogu ukloniti pomoću komercijalnih fizičkih tehnika odvajanja, kao što je destilacija.
Razlozi za niske koncentracije aromatičnih ugljovodonika i naftena u tečnim ugljovodonicima, datim ovim pronalaskom, su dvostruke: prvo, sirovine koje potiču iz Fišer-Tropšovih procesa su inherentno niske u sadržaju molekula koji sadrže prsten, jer ovaj proces pretvaranja primarno, i skoro isključivo, proizvodi linearne lance ugljenika; drugo, pažljiva selekcija katalizatora za pretvaranje ugljovodonika i selekcija uslova primenjenih u procesu formiranja materijala datih ovim pronalaskom uveliko smanjuju formiranje aromata i naftena u toku hidroizomerizacije i katalitičkog deparafiniziranja.
Iako je pogodno da se proizvedu tečni ugljovodonici dati ovim pronalaskom iz materijala izvedenenih iz Fišer-Tropšovog postupka u cilju dobivanja vrlo male koncentracije kontaminanata u proizvedenim fluidima, za formiranje ugljovodoničnih smeša datih ovim pronalaskom mogu se koristiti i drugi parafinski ugljovodonični materijali, kao što su uobičajeni parafinski mazivi rafinati, presovani parafini, presovani parafini oslobođeni ulja, ulja koja se izdvajaju pri znojenju parafina i mazivi destilati hidrokrekovanih proizvoda.
U prošeku, tečne ugljovodonične smeše date ovim pronalaskom su parafinske ugljovodonične komponente koje imaju manje od 10 heksil ili dužih grana na 100 atoma ugljenika. Isto tako tečne ugljovodonične smeše date ovim pronalaskom su parafinske ugljovodonične komponente koje u prošeku imaju više od 16 metil grana na 100 atoma ugljenika. Stupanj hidrodeparafiniziranja koji se koristi da se proizvedu tečni ugljovodonici dati ovim pronalaskom rezultuje u znatnim nivoima izomerizacije dugolančanih parafina u parafinskim (voštanima) sirovinama, rezultujući u parafinskim ugljovodoničnim komponentama sa mnoštvom grana kao što je to opisano u formulama (a) i (b) .
Ugljovodonični fluidi dati ovim pronalaskom nalaze primenu kao osnovne sirovine ulja za podmazivanje ili kao komponente formulisanih ulja za podmazivanje, tj. u kombinaciji sa drugim osnovnim sirovinama ulja za podmazivanje, kao što su, na primer, mineralna ulja, polialfaolefini, estri, polialkileni, alkilovani aromati, hidrokrekovani proizvodi i osnovne sirovine prečišćene rastvaračem.
U drugom oličenju, ovaj pronalazak se odnosi na smešu osnovne sirovine ulja za podmazivanje koja ima parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2> 4) takvi da je:
mereno preko smeše osnovne sirovine ulja za podmazivanje.
Osnovne sirovine ulja za podmazivanje date ovim pronalaskom primarno sadrže izoparafinske komponente sa nominalnim tačkama ključanja od 370°C+ i neobične su u tome što neočekivano pokazuju jedinstvenu kombinaciju visokih indeksa viskoznosti i ekstremno niskih tačaka mržnjenja. U ovoj oblasti tehnike je generalno poznato da su ove dve karakteristike u direktnoj proporciji, tj. sniženje tačke mržnjenja nekog ugljovodoničnog fluida rezultuje u sniženju indeksa viskoznosti, i otuda je sasvim neobično da se istovremeno dobiju ekstremno niska tačka mržnjenja i relativno visok indeks viskoznosti u istom fluidu. Na primer, uobičajene osnovne sirovine mineralnog ulja, kao što su ovde dati primeri za poređenje 3-5, pokazuju relativno niske indekse viskoznosti kada se dublje uroni u oblasti niske tačke mržnjenja (Tabela 1).
Međutim, osnovne sirovine date ovim pronalaskom su okarakterisane ekstremno niskim tačkama mržnjenja (t.m.) nižim ili jednakim -18°C, pogodno nižim ili jednakim -30°C i još pogodnije nižim ili jednakim -40°C, sa kinematičkim viskoznostima (KV) u opsegu od 2,0 cSt do većih od 13 cSt, pogodno od 4 cSt do 8 cSt, pri 100°C i visokim indeksima viskoznosti (VI) od 130-165, pogodno od 140-165 i još pogodnije od 150-165, kao i gore datim vrednostima BI i CH2>4 kao što su gore navedene u formulama (a) i (b) .
Posebno su pogodni produkti dati ovim pronalaskom osnovne sirovine ulja za podmazivanje koje imaju kombinaciju indeksa viskoznosti (VI) i tačke mržnjenja od 130 VI/-66°C do 165 VI/-27°C i pogodnije od 144 VI/-40°C do 165 VI/-27°C.
Katalizatori za konverziju ugljovodonika koji se mogu koristiti u konverziji ovde otkrivenih parafinskih (voštanih) sirovina da se formiraju ugljovodonične komponente date ovim pronalaskom su zeolitni katalizatori, kao što su ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, ofretit, ferierit, zeolit-beta, zeolit-teta, zeolit-alfa, kao što su otkriveni u SAD patentu br. 4.906.350. Ovi katalizatori se koriste u kombinaciji sa metalima VIII grupe, naročito sa paladijumom ili platinom. Metali VIII grupe mogu biti inkorporirani u ove zeolitne katalizatore pomoću uobičajenih tehnika, kao što je jonska izmena.
Postupak proizvodnje osnovnih sirovina ulja za podmazivanje datih ovim pronalaskom može biti okarakterisan kao postupak deparafiniziranja. Ovaj postupak deparafiniziranja može se izvoditi iznad kombinacije katalizatora ili iznad samo jednog katalizatora. Temperature konverzije mogu biti u opsegu od 200°C do 500°C pri pritiscima u opsegu od 500 do 20.000 kPa. Ovaj postupak se izvodi u prisustvu vodonika i parcijalni pritisci vodonika će normalno biti od 600 do 6.000 kPa. Odnos vodonika prema ugljovodoničnoj sirovini za napajanje (brzina cirkulacije vodonika) će normalno biti od 10 do 3.500 n.1.1"<1>(56 do 19.660 SCF/bbl) i prostorna brzina sirovine će normalno biti od 0,1 do 20 LHSV, pogodno od 0,1 do 10 LHSV.
Na primer, konverzija parafinske (voštane) sirovine može se vršiti iznad kombinacije katalizatora Pt/zeolit-beta i Pt/ZSM-23 u prisustvu vodonika. Alternativno tome, postupak proizvodnje inventivnih osnovnih sirovina ulja za podmazivanje može obuhvatati hidroizomerizaciju i deparafiniziranje iznad jednog jedinog katalizatora, kao što je Pt/ZSM-35. U bilo kojem slučaju mogu se dobiti jedinstveni produkti dati ovim pronalaskom.
U drugom oličenju, ovaj pronalazak se odnosi na smešu ulja za podmazivanje koja obuhvata smešu tečnih ugljovodonika koja ima parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2
>4) takvi da je:
mereno preko tečne ugljovodonične smeše kao celine, i opciono, efektivne količine aditiva ulja za podmazivanje, kao što su, na primer, antioksidansi, aditivi protiv habanja, aditivi za ekstremne pritiske, modifikatori frikcije (trenja), poboljšivači indeksa viskoznosti, depresanti tačke mržnjenja, deterdženti, disperzanti, inhibitori korozije, deaktivatori metala, aditivi za kompatibilnost zaptivanja, demulgatori, aditivi protiv penušanja i njihove smeše.
Pregled uobičajenih aditiva maziva je dat u knjiziLubricants and Related Products,od Dietera Klamana, u glavi 9, str. 177-217, Verlag Chemie GmbH (1984), koja ukazuje na neke fenolne ili aromatične amine kao pogodne antioksidanse, benzotriazole kao aditive protiv rđanja, etilendiamine i imidazole kao deaktivatore metala, poliizobutene i polimetakrilate kao poboljšivače indeksa viskoznosti, dugolančane alkil-fenole i dialkilaril-estre ftalne kiseline kao depresante tačke mržnjenja. Kao disperzanti su otkriveni, na primer, polialkilen-sukcinimidi, kao deterdženti jedinjenja kao što su sulfonati, fenolati, sulfurisani fenolati, fosfati i slično. Takođe je otkrivena primena sredstava protiv habanja i aditiva za ekstremne pritiske, koji mogu uključivati organske sulfide, metalne ditiokarbamate, hlorovane parafine i organska fosforna jedinjenja, kao što su metalni ditiofosfati, zatim primena modifikatora trenja kao što su dugolančane masne kiseline, masni alkoholi i masni estri; kao aditivi protiv penušanja su poznati polidimetilsiloksani i etri i estri polietilenglikola, kao aditivi za kompatibilnost zaptivanja su poznata jedinjenja kao aromati, aldehidi, ketoni i estri, kao demulgatori su poznati dinonil-naftalensulfonati, i kao inhibitori korozije su primeri tercijarni amini, amidi masnih kiselina, derivati fosforne kiseline i sulfonske kiseline. Stručnjak verziran u ovoj oblasti će biti svestan da su mnoga od takvih aditivnih jedinjenja poznata u tehnici i mogu se koristiti sa osnovnim uljima datim ovim pronalaskom.
Smeše ulja za podmazivanje date ovim pronalaskom mogu sadržati druge osnovne sirovine ulja za podmazivanje, kao što su mineralna ulja, polialfaolefini, estri, polialkileni, alkilovani aromati, hidrokrekovani proizvodi i osnovne sirovine prečišćene pomoću rastvarača, u kombinaciji sa ovde opisanim parafinskim ugljovodoničnim komponentama. Parafinske ugljovodonične smeše date ovim pronalaskom mogu se koristiti kao glavni deo osnovnog ulja za smešu ulja za podmazivanje, sa drugim više uobičajenim osnovnim sirovinama ulja za podmazivanje koje su u to dodate, ili se mogu koristiti kao aditiv u kombinaciji sa glavnom količinom neke druge osnovne sirovine ulja za podmazivanje. Međutim, pogodno je da tečne ugljovodonične smeše date ovim pronalaskom budu prisutne u nivoima koncentracije od najmanje 5 tež. % u odnosu na ukupnu smešu osnovne sirovine ulja za podmazivanje.
Primeri
U sledećim primerima su uslovi hidroizomerizacije i reakcije katalitičkog deparafiniziranja varirani tako da se dobiju željeni produkti, pri čemu su tipični uslovi bili u opsezima, ali nisu na njih ograničeni, od 200-370°C, 400-2000 psig, 0,50-2,0 hr"<1>LHSV i 1900-5000 scf/B (standardnih kubnih stopa na barel) H2na ulazu reaktora.
Fizičke osobine osnovne sirovine ulja za podmazivanje
Primeri 1-4
Hidrogenuizovan Fišer-Tropšov parafin (Paraflint 80) je hidrodeparafiniziran u prisustvu vodonika iznad kombinacije hidroizomerizacionog katalizatora Pt/zeolit-beta i selektivnog katalizatora za deparafiniziranje Pt/ZSM-23. Pod pojačavajuće oštrim uslovima prerade dobivena su četiri različita ugljovodonična fluida koji imaju vrednosti kinematičke viskoznosti (KV), indeksa viskoznosti (VI) i tačke mržnjenja (t.m.) kao što je dato u Tabeli 1. Primer 4 je primer dat ovim pronalaskom.
Primeri 5i6
Hidrogenizovan i parcijalno izomerizovan srednji destilat sinteznog parafinskog rafinata (Shell MDS ili "SMDS") je hidrodeparafiniziran u prisustvu vodonika iznad kombinacije katalizatora koji su upotrebljeni u primerima 1-4. Pod pojačavajuće oštrim uslovima prerade dobivena su dva različita ugljovodonična fluida koji imaju vrednosti kinematičke viskoznosti (KV), indeksa viskoznosti (VI) i tačke mržnjenja (t.m.) kao što je dato u Tabeli 1. Primer 6 je primer dat ovim pronalaskom.
Primeri 7-9
Osnovna sirovina Shell MDS iz primera 5 i 6 je hidrodeparafinizirana iznad sintetičkog ferierita u prisustvu vodonika pod varirajuće oštrim uslovima prerade tako da su dobivena tri različita ugljovodonična fluida koji imaju vrednosti kinematičke viskoznosti (KV), indeksa viskoznosti (VI) i tačke mržnjenja (t.m.) kao što je dato u Tabeli 1. Svi primeri 7-9 su primeri dati ovim pronalaskom.
Primer 10
Parafinska sirovina koja je upotrebljena u primerima 1-4 je hidrodeparafinizirana iznad Pt/ZSM-48 u prisustvu vodonika tako da je proizveden ugljovodonični fluid koji ima vrednosti kinematičke viskoznosti (KV), indeksa viskoznosti (VI) i tačke mržnjenja (t.m.) kao što je dato u Tabeli 1. Primer 10 je primer dat ovim pronalaskom.
Primeri za poređenje 1, 2i6
Komercijalno dobivene polialfaolefinske osnovne sirovine sa vrednostima kinematičke viskoznosti (KV) 3,87 cST i 5,51 cSt pri 100°C su okarakterisane sa tačkama mržnjenja <-65°C i indeksima viskoznosti (VI) 130 (primer za poređenje 1) odnosno 135 (primer za poređenje 2). Takođe je uključen i komercijalni polialfaolefin visokog stepena viskoznosti od 150 cSt KV pri 100°C (primer za poređenje 6).
Primeri za poređenje 3-5
Takođe je procenjeno nekoliko komercijalno dobivenih osnovnih sirovina izvedenih iz frakcija hidrokrekovanog sirovog ulja. Ove uključuju:a.-18°C tačka mržnjenja, 5,1 cSt KV@100°C, 147 VI Shell XHVI osnovna sirovina izvedena iz hidroizomerizacije presovanog parafina (primer za poređenje 3);b.4,0 cSt KV@100°C, 114 VI Yukong 100N osnovna sirovina okarakterisana tačkom mržnjenja od -15°C (primer za poređenje 4) ic.6,9 cSt KV@100°C, 102 VI Chevron RLOP 240 N osnovna sirovina koja je takođe okarakterisana tačkom mržnjenja od -15°C (primer za poređenje 5).
Na donjoj Tabeli 1 su poređene tipične fizičke osobine različitih komercijalnih osnovnih sirovina ulja za podmazivanje sa osobinama inventivnih Fišer-Tropšovih izomerata sa ultra niskom tačkom mržnjenja.
Slika 1 je grafičko poređenje performansi simulacije hladnog startovanja sa hladnim delovima (CCS) za tipičnu hidroprerađenu ugljovodoničnu osnovnu sirovinu ulja za podmazivanje (XHVI) i dve bazne sirovine date ovim pronalaskom. CCS testiranje je izvršeno prema ASTM metodi D5392 koja se koristi da se meri prividna viskoznost motornih ulja. CCS viskozimetar meri dinamičku viskoznost fluida pri niskoj temperaturi i niskom stupnju smicanja i stresa, čime se simulira protok ulja u karteru (kućištu radilice) motora pri uslovima niskotemperaturnog startovanja (krenking). Podaci sa slike 1 pokazuju da osnovne sirovine ulja za podmazivanje date ovim pronalaskom imaju superiorne niskotemperaturne viskozimetrijske osobine.
Merenje karakteristika grananja
Indeks grananja ( BI)
Za svaku osnovnu sirovinu prikazanu na Tabeli 1 snimljeni su 359,88 MHz<X>H-NMR spektri na spektrometru Bruker 360 MHz AMX uz primenu 10%-nih rastvora u CDC13. TMS je bio interni standard za hemijsko pomeranje. Rastvarač CDC13daje pik lociran na 7,28 ppm. Svi spektri su dobiveni pod kvantitativnim uslovima koristeći puls od 90 stepeni (10,9 fisek) , vreme kašnjenja pulsa je bilo 30 sek, što je najmanje pet puta najduže vreme relaksacije vodonične spinske rešetke (Ti) i 120 skenova da se osiguraju dobri odnosi signala prema šumu.
H atomi su definisani prema sledećim oblastima: 9,2-6,2 ppm vodonici na aromatičnim prstenovima, 6,2-4,0 ppm vodonici na olefinskim atomima
ugljenika,
4.0- 2,1 ppm benzilni vodonici u a-položaju
prema aromatičnim prstenovima, 2.1- 1,4 ppm parafinski CH metinski vodonici, 1,4-1,05 ppm parafinski CH2metilenski vodonici,
1,05-0,5 ppm parafinski CH3metil vodonici.
Indeks grananja (BI) je izračunat kao odnos procen-ta ne-benzilnih metil vodonika u opsegu od 0,5 do 1,05 ppm prema ukupnom broju ne-benzilnih alifatičnih vodonika u opsegu od 0,5 do 2,1 ppm. Rezultati dobiveni iz ovih<1>H-NMR-analiza su pregledno dati na donjoj Tabeli 2.
Blizina grananja ( CH2>4_)
Za svaku osnovnu sirovinu prikazanu na Tabeli 1 snimljeni su 90,5 MHz<13>C-NMR singl pulsni i 135 DEPT (Distortionless Enhancement by Polarization Transfer (u slobodnom prevodu "pojačanje (signala) prenosom polarizacije bez (fazne) deformacije")) NMR spektar na spektrometru Bruker 360 MHz AMX uz primenu 10%-nih rastvora u CDC13. TMS je bio interni standard za hemijsko pomeranje. Rastvarač CDCI3daje triplet lociran na 77,23 ppm u<13>C-NMR~spektru. Svi singl pulsni spektri su dobiveni pod kvantitativnim uslovima koristeći pulseve od 45 stepeni (6,3 |isek) , vreme kašnjenja pulsa je bilo 60 sek, što je najmanje pet puta najduže vreme relaksacije ugljenične spinske rešetke (Ti) , tako da se osigura potpuna relaksacija uzorka, 200 skenova da se osiguraju dobri odnosi signala prema šumu, i WALTZ-16 protonsko dekuplovanje.
Iz 135 DEPT<13>C-NMR eksperimenta su identifikovani tipovi atoma ugljenika: CH3fCH2i CH. Glavna CH2rezonancija u svim<13>C-NMR spektrima na -29,8 ppm je prouzrokovana ekvivalentno periodičnim metilenskim ugljenicima koji su četiri ili više atoma ugljenika udaljeni od krajnje grupe ili grane (CH2>4). Tipovi grana su određeni primarno na bazi<13>C hemijskih pomeranja za metil atom ugljenika na kraju grane ili metilenski ugljenik za jedan udaljen od metila na toj grani. Blizina grana, kao što je to ukazano sa CH2>4, i tip ugljenika su sumarno dati na Tabeli 3.
Na sledećoj Tabeli 4 su poređene karakteristike grananja i tačke mržnjenja izoparafinskih komponenata osnovnih smeša iz primera, kao što je otkriveno u Tabelama 1-3.
Osnovne sirovine date ovim pronalaskom mogu se diferencirati od drugih ugljovodoničnih osnovnih sirovina opsegom grananja kao što je ukazano pomoću BI i blizine grananja što je ukazano sa CH2>4. Ovi otisci prsta njihovog sastava su dati grafički radi potpomoganja definisanja jedinstvenih regiona u ovom dvodimenzionalnom kompozicionom prostoru kao što je ilustrovano na slici 2 (levi kvadrant).
Iz slike 2 se vidi da su karakteristike grananja izoparafinskih osnovnih smeša datih ovim pronalaskom unutar jednog jedinstvenog regiona. Specifično, ova smeša se može opisati kao smeša koja obuhvata smeše parafinskih ugljovodoničnih komponenata u kojima su opseg grananja, meren procentom metilnih vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grananja (CH2>4) takvi da je:
Slika 3 je grafičko poređenje dinamičkih viskoznosti (DV@-40°C) merenih CCS metodom i kinematičkih viskoznosti (KV@100°C) različitih ugljovodoničnih fluida uključujući i one date ovim pronalaskom. Fluidi dati ovim pronalaskom su označeni kao "FTWI" (Fišer-Tropšov voštani (parafinski) izomerat), dok su uobičajene hidrokrekovane osnovne sirovine označene kao "HDC". Posebno, tačke podataka (vrednosti) HDC predstavljaju primere za poređenje 3-5 date ovom specifikacijom.
Iz podataka datih na slici 3 je jasno da FTWI fluidi dati ovim pronalaskom imaju znatno poboljšane niskotemperaturske karakteristike viskoznosti u poređenju sa ovim karakteristikama uobičajenih (konvencionalnih) HDC fluida iz ranije oprakse. Treba primetiti da svi tečni ugljovodonični fluidi dati ovim pronalaskom padaju ispod isprekidane (tačkaste) linije na dijagramu i otuda se mogu opisati sledećom jednačinom:
Pošto je ovaj pronalazak tako opisan očigledno je da se isti može varirati na mnogo načina. Takve varijacije se ne trebaju smatrati kao odstupanja od duha i opsega ovog pronalaska i sve takve modifikacije, koje bi bile očigledne stručnjaku u ovoj oblasti, uključene su unutar opsega sledećih zahteva.

Claims (21)

1. Tečna ugljovodonična smeša, naznačena time, što obuhvata parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je: mereno preko pomenute tečne ugljovodonične smeše kao celine.
2. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što sadrži manje od 0,1 tež. % aromatičnih ugljovodonika, manje od 20 tež. ppm jedinjenja koja sadrže azot, i manje od 20 tež. ppm jedinjenja koja sadrže sumpor.
3. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što je tačka mržnjenja smeše niža od -18°C.
4. Tečna ugljovodonična smeša prema zahtevu 3, naznačena time, što je tačka mržnjenja smeše niža od -30°C.
5. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što pomenute parafinske ugljovodonične komponente imaju BI > 25,4 i (CH2>4) < 22,5.
6. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što pomenute parafinske ugljovodonične komponente imaju nominalne tačke ključanja od 370°C+.
7. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što pomenute parafinske ugljovodonične komponente obuhvataju u prošeku manje od 10 heksil- ili dužih grana na 100 atoma ugljenika.
8. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što pomenute parafinske ugljovodonične komponente obuhvataju u prošeku više od 16 metil grana na 100 atoma ugljenika.
9. Tečna ugljovodonična smeša prema zahtevu 1, naznačena time, što je kombinacija dinamičke viskoznosti, merene sa CCS pri -40°C, i kinetičke viskoznosti merene na 100°C pomenutog tečnog ugljovodoničnog fluida predstavljena formulom: (c) DV@_40°C< 2900 (KV@100oc) - 7000.
10. Osnovna smeša ulja za podmazivanje, naznačena time, što obuhvata parafinske ugljovodonične komponente u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je: mereno preko pomenute osnovne smeše ulja za podmazivanje kao celine.
11. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što sadrži manje od 0,1 tež. % aromatičnih ugljovodonika, manje od 20 tež. ppm jedinjenja koja sadrže azot i manje od 20 tež. ppm jedinjenja koja sadrže sumpor.
12. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što je tačka mržnjenja smeše niža od -18°C.
13. Osnovna smeša ulja za podmazivanje prema zahtevu 12, naznačena time, što je tačka mržnjenja smeše niža od -30°C.
14. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što pomenute parafinske ugljovodonične komponente imaju BI > 25,4 i (CH2>4)< 22,5.
15. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što pomenute parafinske ugljovodonične komponente imaju nominalne tačke ključanja od 370°C+.
16. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što pomenute parafinske ugljovodonične komponente obuhvataju u prošeku manje od 10 heksil- ili dužih grana na 100 atoma ugljenika.
17. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što pomenute parafinske ugljovodonične komponente obuhvataju u prošeku više od 16 metil grana na 100 atoma ugljenika.
18. Osnovna smeša ulja za podmazivanje prema zahtevu 10, naznačena time, što je kombinacija dinamičke viskoznosti, merene sa CCS pri -40°C, i kinetičke viskoznosti merene na 100°C pomenutog tečnog ugljovodoničnog fluida predstavljena formulom:
19. Osnovna smeša ulja za podmazivanje, naznačena time, što obuhvata tečnu ugljovodoničnu smešu koja ima smešu parafinskih ugljovodoničnih komponenata u kojima su opseg grananja, meren procentom metil vodonika (BI), i blizina grananja, merena procentom periodičnih metilenskih ugljenika, koji su četiri ili više ugljenika udaljeni od krajnje grupe ili grane (CH2>4) takvi da je: mereno preko pomenute tečne ugljovodonične smeše kao celine, i opciono, efektivne količine aditiva ulja za podmazivanje odabranih iz grupe koja se sastoji od antioksidanasa, aditiva protiv habanja, aditiva za ekstremne pritiske, modifikatora frikcije (trenja), poboljšivača indeksa viskoznosti, depresanata tačke mržnjenja, deterdženata, disperzanata, inhibitora korozije, deaktivatora metala, aditiva za kompatibilnost zaptivanja, demulgatora, aditiva protiv penušanja i njihovih smeša.
20. Osnovna smeša ulja za podmazivanje iz zahteva 19, naznačena time, što dalje obuhvata osnovnu sirovinu ulja za podmazivanje odabranu iz grupe koja se sastoji od mineralnih ulja, polialfaolefina, estara, polialkilena, alkilovanih aromata, hidrokrekovanih proizvoda i osnovnih sirovina prečišćenih rastvaračem.
21. Osnovna smeša ulja za podmazivanje iz zahteva 20, naznačena time, što je pomenuta tečna ugljovodonična smeša prisutna u koncentraciji od najmanje 5 tež. % u odnosu na ukupnu osnovnu smešu ulja za podmazivanje.
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