NO128873B - - Google Patents

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NO128873B
NO128873B NO03853/70A NO385370A NO128873B NO 128873 B NO128873 B NO 128873B NO 03853/70 A NO03853/70 A NO 03853/70A NO 385370 A NO385370 A NO 385370A NO 128873 B NO128873 B NO 128873B
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oil
per molecule
atoms per
alcohol
hydrocarbon composition
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NO03853/70A
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Norwegian (no)
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R Price
M Kingsland
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Exxon Research Engineering Co
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Publication of NO128873B publication Critical patent/NO128873B/no

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups

Description

Flytende hydrokarbonsammensetninger med nedsatt hellepunkt, Liquid hydrocarbon compositions with a reduced pour point,

samt middel for nedsettelse av hellepunktet. as well as means for lowering the pour point.

Foreliggende oppfinnelse angår flytende hydrokarbon-brennstoffer og -oljesammensetninger som inneholder en strømnings- eller flytforbedrende tilsetning som nedsetter hellepunktet og således forbedrer strømningshastigheten for brennstoffet eller oljen. The present invention relates to liquid hydrocarbon fuels and oil compositions which contain a flow or flow-improving additive which lowers the pour point and thus improves the flow rate of the fuel or oil.

Man kjenner mange strømningsforbedrende tilsetninger og hellepunktsenkende stoffer, men mange har, når de er tilsatt brennstoffet eller smøreoljer en begrenset virkning, idet hellepunktet etter en viss tid synes å gå tilbake mot hellepunktet for ubehandlet olje. Denne tilbakegang (Tegresjon) er naturligvis en ulempe og begrenser verdien av disse strømningsforbedrende og hellepunktsenkende tilsetninger. Man har nå funnet strømningsforbedrende og hellepunktsenkende tilsetninger som i det vesentlige ikke viser slik tilbakegang, i det minste kombinert med restoljeholdige oljer og brennstoffer, skiferoljer eller flashdestillater. Many flow-improving additives and pour point-lowering substances are known, but many have a limited effect when added to fuel or lubricating oils, as the pour point seems to return to the pour point of untreated oil after a certain time. This regression (Tegression) is naturally a disadvantage and limits the value of these flow-improving and pour-point-lowering additives. Flow-improving and pour-point-lowering additives have now been found which essentially do not show such a decline, at least when combined with residual oil-containing oils and fuels, shale oils or flash distillates.

Ifølge foreliggende oppfinnelse er det tilveiebragt en flytende hydrokarbonsammensetning med nedsatt hellepunkt, og denne sammensetning er kjennetegnet ved at den som hovedkomponent inneholder en flashdestillert brenselolje eller en råolje eller 'skifcrolje, eller fortrinnsvis en restoljeholdig olje, og 0,0001 til 10%, fortrinnsvis 0,0005 til 0,5 vektprosent, på basis av brennstoffets eller oljens vekt, av et reaksjonsprodukt mellom a) en alkohol inneholdende minst 16, fortrinnsvis 20 til 26 C-atomer pr. molekyl og According to the present invention, a liquid hydrocarbon composition with a reduced pour point is provided, and this composition is characterized by the fact that it contains as its main component a flash-distilled fuel oil or a crude oil or 'shale oil, or preferably a residual oil-containing oil, and 0.0001 to 10%, preferably 0 .0005 to 0.5 percent by weight, based on the weight of the fuel or oil, of a reaction product between a) an alcohol containing at least 16, preferably 20 to 26 C atoms per molecule and

b) en kopolymer av komonomere omfattende (1) en etylenisk umettet dikarboksylsyre eller -anhydrid eller -derivat, og (2) minst ett b) a copolymer of comonomers comprising (1) an ethylenically unsaturated dicarboxylic acid or anhydride or derivative, and (2) at least one

alfa-olefin som inneholder minst 20 og fortrinnsvis 20 til 50 C-atomer pr. molekyl. alpha-olefin containing at least 20 and preferably 20 to 50 C atoms per molecule.

Videre er det ifølge oppfinnelsen tilveiebragt et middel for nedsettelse av hellepunktet for den flytende hydrokarbonsammensetning og dette middel består av det ovenfor definerte reaksjonsprodukt. Furthermore, according to the invention, an agent is provided for lowering the pour point of the liquid hydrocarbon composition and this agent consists of the reaction product defined above.

Det er sterkt foretrukket i henhold til oppfinnelsen at hydro-karbonet er restholdig brennstoff. Dette restholdige brennstoff defineres som brennstoff inneholdende residuum fra destillasjon av råolje eller skiferolje eller blandinger av disse. Vanligvis inneholder det restholdige brennstoff mellom 10 og 100%, f.eks. 35 til 100% residuum på vektbasis, hvilket residuum fortrinnsvis koker over 315°C ved 1 atmosfæres trykk, og dette brennstoff vil vanligvis ha kinematiske viskositeter på mellom 10 og 3.500 cS ved 38°C. Imidlertid kan viskositeten for en del særlig voksholdige brennstoffer være vanskelig å måle nøyaktig ved 38°C, og det er velkjent på området at viskositeten for slike brennstoffer regnes ut etter måling av viskositeten ved høyere temperatur. Viskositeten ved 38°C får man ved ekstrapolering ut fra et R.E.F.U.T.A.S. viskositets-temperatur-dia-gram. Den ekstrapolerte kinematiske viskositet vil da falle innen-for det ønskede område ved 38°C. R.E.F.U.T.A.S.-temperatur-viskosi-tets-diagrammet ble satt opp av CI. Kelly M.Sc. Tech, F.I.C., M.Inst.Pet., A.M.I.A.E., reservert copyright i Storbritannia og U.S.A. av Baird and Tatlock (London) Limited, 14-17 Cross Street, Hatton Garden, London, E.C.l. Brennstoff med kinematisk viskositet på mellom 15 og 1500 cS ved 38°C foretrekkes, og likeledes brennstoffer hvor minst 30% og fortrinnsvis minst 60 vektprosent av brenn- It is strongly preferred according to the invention that the hydrocarbon is residual fuel. This residual fuel is defined as fuel containing residue from the distillation of crude oil or shale oil or mixtures of these. Usually it contains residual fuel between 10 and 100%, e.g. 35 to 100% residue by weight, which residue preferably boils above 315°C at 1 atmosphere pressure, and this fuel will usually have kinematic viscosities of between 10 and 3,500 cS at 38°C. However, the viscosity of some particularly waxy fuels can be difficult to measure accurately at 38°C, and it is well known in the field that the viscosity of such fuels is calculated after measuring the viscosity at a higher temperature. The viscosity at 38°C is obtained by extrapolating from a R.E.F.U.T.A.S. viscosity-temperature diagram. The extrapolated kinematic viscosity will then fall within the desired range at 38°C. The R.E.F.U.T.A.S. Temperature Viscosity Chart was compiled by CI. Kelly M.Sc. Tech, F.I.C., M.Inst.Pet., A.M.I.A.E., UK and U.S. copyright reserved. of Baird and Tatlock (London) Limited, 14-17 Cross Street, Hatton Garden, London, E.C.l. Fuel with a kinematic viscosity of between 15 and 1500 cS at 38°C is preferred, and likewise fuels where at least 30% and preferably at least 60% by weight of fuel

stoffet koker over 260°C ved atmosfaeretrykk. the substance boils above 260°C at atmospheric pressure.

De restholdige brennstoffer som fortrinnsvis anvendes omfatter således lette, middels og tunge brennstoffer samt tankoljer eller brenseloljer hvor viskositeten ligger mellom ca. 15 - 2000 The residual fuels that are preferably used therefore include light, medium and heavy fuels as well as tank oils or fuel oils where the viscosity is between approx. 15 - 2000

cS ved 38°C, men vanligvis vil imidlertid maksimalviskositeten ligge på omkring 1500 cS ved 38°C. Eksempler på egnede brennstoffer er beskrevet i punkt 3 Industrial and Marine Fuels of BS 2869: 1957. cS at 38°C, but usually, however, the maximum viscosity will be around 1500 cS at 38°C. Examples of suitable fuels are described in point 3 Industrial and Marine Fuels of BS 2869: 1957.

Egnede brennstoffer omfatter også "flash-destillerte brennstoffer" som er definert som destillater som fåes ved flashdestiller-ing ved redusert trykk av det residuum som blir tilbake etter destillasjon av råolje ved atmosfaeretrykk. Slikt brennstoff fremstilles ved å destillere under atmosfaeretrykk en råolje til en kolonne-bunn-temperatur på ca. 350°C, hvilket da etterlater en atmosfærisk rest eller residuum som da ved "flashing" under meget redusert trykk opp-deles i et flash-destillat og et vakuum-residuum. Ved "flash-destillasjon" innføres kontinuerlig forvarmet charge i et flashkammer hvor fordampning finner sted under konstante likevektsforhold. Det fjernes kontinuerlig gassformige og flytende produkter. Fraksjonering finner ikke i særlig grad sted ved flashing. Den temperatur som flashingen kan utføres under begrenses av mulighet for krakking og forkulling. Disse sidereaksjoner begynner hvis temperaturen overstiger 200°C. Flashing gjennomføres ved meget redusert trykk for å oppnå høyt ut-bytte av destillat fra en gitt mengde atmosfærisk residuum. Suitable fuels also include "flash-distilled fuels" which are defined as distillates obtained by flash distillation at reduced pressure of the residue that remains after distillation of crude oil at atmospheric pressure. Such fuel is produced by distilling a crude oil under atmospheric pressure to a column-bottom temperature of approx. 350°C, which then leaves an atmospheric residue or residue which is then split into a flash distillate and a vacuum residue during "flashing" under very reduced pressure. In "flash distillation", a continuously preheated charge is introduced into a flash chamber where evaporation takes place under constant equilibrium conditions. Gaseous and liquid products are continuously removed. Fractionation does not take place to a particular extent during flashing. The temperature at which the flashing can be carried out is limited by the possibility of cracking and charring. These side reactions begin if the temperature exceeds 200°C. Flashing is carried out at very reduced pressure to achieve a high yield of distillate from a given amount of atmospheric residue.

Man kan også bruke skiferoljer og råoljen selv. Vanligvis er hellepunktet for råoljer høyere enn -23°C. You can also use shale oils and the crude oil itself. Generally, the pour point of crude oils is higher than -23°C.

Egnede etylenisk umettede dikarboksylsyrer omfatter maleinsyre, fumarsyre, mesakonsyre, citrakonsyre, itakonsyre, trans- og cis-glutakonsyrer. De tilsvarende anhydrider (når disse eksisterer) kan også brukes. Suitable ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, trans- and cis-glutaconic acids. The corresponding anhydrides (when these exist) can also be used.

Imidlertid foretrekkes det å anvende maleinsyreanhydrid eller et derivat av denne. However, it is preferred to use maleic anhydride or a derivative thereof.

Slike derivater'omfatter stoffer med den generelle formel Such derivatives' include substances of the general formula

hvor og R2 er hydrogen, et halogen eller en alkylgruppe med 1 where and R2 is hydrogen, a halogen or an alkyl group with 1

til 6 C-atomer (f.eks. metyl, etyl eller butyl), og X er oksygen. Egnede eksempler på slike derivater er metyl-maleinsyreanhydrid, dimetyl-maleinsyreanhydrid, etyl-maleinsyreanhydrid, klormalein-syreanhydrid, eller diklormaleinsyreanhydrid. Et annet maleinsyreanhydrid-derivat som kan brukes er maleinsyre. to 6 C atoms (eg methyl, ethyl or butyl), and X is oxygen. Suitable examples of such derivatives are methyl maleic anhydride, dimethyl maleic anhydride, ethyl maleic anhydride, chloromaleic anhydride or dichloromaleic anhydride. Another maleic anhydride derivative that can be used is maleic acid.

Den etylenisk umettede dikarboksylsyre eller -anhydrid eller -derivat omsettes med et alfaolefin som inneholder minst 20 C-atomer pr. molekyl. Selv om det ikke er noen øvre grense for antall C-atomer pr. molekyl, vil i praksis olefiner mellom 20 og 50, spesielt mellom 22 og 30 C-atomer pr. molekyl være særlig egnet. Man kan bruke blandinger av alfaolefiner, f.eks. en C->2 til C2g-blanding. Egnede a-olefiner er således cos-l-en, docos-l-en, tetracos-l-en, heksacos-l-en og oktacos-l-en. The ethylenically unsaturated dicarboxylic acid or anhydride or derivative is reacted with an alpha olefin containing at least 20 C atoms per molecule. Although there is no upper limit to the number of C atoms per molecule, in practice olefins will have between 20 and 50, especially between 22 and 30 C atoms per molecule be particularly suitable. Mixtures of alpha olefins can be used, e.g. a C->2 to C2g mixture. Suitable α-olefins are thus cos-1-ene, docos-1-ene, tetracos-1-ene, hexacos-1-ene and octacos-1-ene.

Omsetningen mellom dikarboksylsyren, -anhydridet eller -deri-vatet og a-olefinet kan med fordel skje ved å blande a-olefinet med minst 0,5 mol og fortrinnsvis 1 til 2 mol syre, anhydrid eller derivat og oppvarme blandingen til en temperatur på minst 100°C, fortrinnsvis minst 140°C. Vanligvis brukes en katalysator som t-butyl-hydroperoksyd eller di-t-butyl-peroksyd. Sluttproduktet har etter forestring etc. en antallsmidlere molekylvekt på 500 til 50.000, vanligvis 500 til 20.000 og mest egnet 1000 til 1500. The reaction between the dicarboxylic acid, anhydride or derivative and the α-olefin can advantageously take place by mixing the α-olefin with at least 0.5 mol and preferably 1 to 2 mol of acid, anhydride or derivative and heating the mixture to a temperature of at least 100°C, preferably at least 140°C. Usually a catalyst such as t-butyl hydroperoxide or di-t-butyl peroxide is used. The final product, after esterification etc., has a number average molecular weight of 500 to 50,000, usually 500 to 20,000 and most suitable 1,000 to 1,500.

Dét således fremstilte reaksjonsprodukt omsettes med en alkohol eller et amin som inneholder minst 16 C-atomer, fortrinnsvis opp til 26 C-atomer pr. molekyl. Alkoholen kan være rettkjedet eller forgrenet, men de mest gunstige alkoholer er alifatiske i det vesentlige rettkjedete monohydroksyalkoholer som inneholder fra 20 til 26 C-atomer pr. molekyl. Slike alkoholer er eicosanol, C22-oksoalkohol, tetracosanol, og kan omfatte blandinger av slike alkoholer, f.eks. behenylalkohol. The thus produced reaction product is reacted with an alcohol or an amine containing at least 16 C atoms, preferably up to 26 C atoms per molecule. The alcohol may be straight-chain or branched, but the most favorable alcohols are aliphatic, essentially straight-chain monohydroxy alcohols containing from 20 to 26 C atoms per molecule. Such alcohols are eicosanol, C22-oxo alcohol, tetracosanol, and may include mixtures of such alcohols, e.g. behenyl alcohol.

Mengden reaksjonsprodukt, dvs. additiv, som tilsettes brennstoffet eller oljen bør fortrinnsvis være mellom 0,0001% og 10%, f.eks. mellom 0,0005 og 0,5 vektprosent, basert på vekten av rést-holdig brennstoff, flash-destillat, skiferolje eller råolje. The amount of reaction product, i.e. additive, which is added to the fuel or oil should preferably be between 0.0001% and 10%, e.g. between 0.0005 and 0.5 percent by weight, based on the weight of residual fuel, flash distillate, shale oil or crude oil.

Fremstilling 1 Production 1

Til en 500 ml, 5-halskolbe for polymerisasjon forsynt med vannkjøler, rører og termometer tilsatte man: 56 deler maleinsyreanhydrid og 200 deler C22_2g-l-olefin-fraksjon, med et jodtall på 76 g/100 g. Komponentene ble oppvarmet til 145°C og di-t-butyl-peroksyd tilsatt i en mengde på 0,5 deler pr. time i løpet av 1 time og 1 kvarter. Reaksjonen ble avsluttet etter 1,5 timer ved tilsetning av 1000 deler xylen. Kopolymeren hadde et forsåp-ningstall på 255 mg KOH pr. g og en molekylvekt på 1200. Den kopolymere ble di-forestret ved tilsetning av 358 deler alkohol (behenylalkohol) med følgende sammensetning: C^g 16%, C2q 15%, To a 500 ml, 5-neck polymerization flask equipped with a water cooler, stirrer and thermometer was added: 56 parts of maleic anhydride and 200 parts of C22_2g-1-olefin fraction, with an iodine number of 76 g/100 g. The components were heated to 145° C and di-t-butyl peroxide added in an amount of 0.5 parts per hour during 1 hour and 1 quarter. The reaction was terminated after 1.5 hours by the addition of 1000 parts of xylene. The copolymer had a saponification number of 255 mg KOH per g and a molecular weight of 1200. The copolymer was di-esterified by adding 358 parts of alcohol (behenyl alcohol) with the following composition: C^g 16%, C2q 15%,

C27 69%, samt 5 deler p-toluen-sulfonsyre. Oppløsningen ble kokt under tilbakeløp i 8 timer, reaksjonsvannet ble oppfanget i en Dean og Stark vann-oppfanger. Produktet ble opparbeidet ved å avdampe xylenet under nedsatt trykk. Det di-forestrede.produkt hadde en antallsmidlere molekylvekt på omtrent 2750. C27 69%, as well as 5 parts of p-toluenesulfonic acid. The solution was refluxed for 8 hours, the water of reaction was collected in a Dean and Stark water trap. The product was worked up by evaporating the xylene under reduced pressure. The di-esterified product had a number average molecular weight of about 2750.

Fremstilling 2 og 5 Production 2 and 5

På samme måten som under fremstilling 1 ble de følgende kopolymere fremstilt (tabell 1) . C.jQ + -olefin er et kommersielt produkt med en molekylvekts-fordeling på 25% a-olefiner i ^ 20~^ Z0 områ<iet og 75% a-olefiner i C3q-C5q området. In the same way as during preparation 1, the following copolymers were prepared (table 1). C.jQ + -olefin is a commercial product with a molecular weight distribution of 25% α-olefins in the ^ 20~^ Z0 range and 75% α-olefins in the C3q-C5q range.

De kopolymere ble di-forestret under lignende betingelser som for fremstilling 1: The copolymers were di-esterified under similar conditions as for preparation 1:

Fremstilling 4 Manufacturing 4

Man fremstilte monoestere av alle kopolymere på lignende måte, bortsett fra at halvparten av alkoholmengden ble forbrukt under forestringstrinnet og det ikke ble tilsatt noe p-toluen-sulfonsyre. Monoestrene fremstilt fra kopolymerene fra Fremstilling 1 og 2 hadde en antallsmidlere molekylvekt på henholdsvis 2000 og 4000. Monoesters of all copolymers were prepared in a similar manner, except that half of the alcohol was consumed during the esterification step and no p-toluenesulfonic acid was added. The monoesters prepared from the copolymers from Preparation 1 and 2 had a number average molecular weight of 2000 and 4000 respectively.

Eksempel 1 Example 1

Additiver som fremstilt under punktene 1, 2, 3 og 4 ble blandet sammen med to restoljeholdige brennstoffer A og B ved om-røring i 1 time ved 82°C. Hellepunktet for blandingene ble deretter målt (admiralitetets metode 7). Additives as prepared under points 1, 2, 3 and 4 were mixed together with two residual oil-containing fuels A and B by stirring for 1 hour at 82°C. The pour point of the mixtures was then measured (Admiralty Method 7).

Brenselolje A var en restolje fremstilt fra nordafrikansk råolje ved destillasjon til en slutt-temperatur på 377°C. Den inneholdt 1001 restolje og hadde hellepunkt på 41°C. Fuel oil A was a residual oil produced from North African crude oil by distillation to a final temperature of 377°C. It contained 1001 residual oil and had a pour point of 41°C.

Brenselolje B var en restolje fremstilt fra 30 vektprosent solarolje og 70 vektprosent restolje fra destillasjon av Libya-råolje opp til en slutt-temperatur på 344°C. Brenseloljen hadde et hellepunkt på 35°C. Fuel oil B was a residual oil produced from 30 weight percent solar oil and 70 weight percent residual oil from the distillation of Libyan crude oil up to a final temperature of 344°C. The fuel oil had a pour point of 35°C.

Resultatene var: The results were:

Hellepunktet for restoljer (admiralitetets metode 7) er en modifisert hellepunktsbestemmelse utviklet av det britiske admirali-tet for å angi det maksimale øvre hellepunkt som kan bestemmes ved lengre tids lagring av restoljer. Prøven består i først å oppvarme den til 95°C, dele den i mindre prøver, luftkjøle og deretter sjokk-kjøle. Deretter blir de forskjellige prøver oppvarmet med forskjellige oppvarmingstemperaturer og -hastigheter. Deretter bestemmes det øvre hellepunkt for hver prøve og maksimalverdien av hellepunktet. Fremgangsmåten er beskrevet i "Journal of the Institute of Petroleum", 1960, bind 46, side 189. The pour point for residual oils (admiralty's method 7) is a modified pour point determination developed by the British Admiralty to indicate the maximum upper pour point that can be determined during long-term storage of residual oils. The test consists of first heating it to 95°C, dividing it into smaller samples, air-cooling and then shock-cooling. The different samples are then heated at different heating temperatures and rates. The upper pour point for each sample and the maximum value of the pour point are then determined. The procedure is described in the "Journal of the Institute of Petroleum", 1960, volume 46, page 189.

Tabellen illustrerer at resultater oppnådd med monoestere av additiver i henhold til oppfinnelsen ofte er vesentlig bedre enn resultater oppnådd med diestere av C-^g-produktet. The table illustrates that results obtained with monoesters of additives according to the invention are often significantly better than results obtained with diesters of the C-^g product.

Dette er en overraskende fordel som man oppnår ved å velge og benytte additiver i henhold til oppfinnelsen. Om ønsket får man dessuten den fordel at det kan brukes mindre av den langkjedede for-estringspartner. This is a surprising advantage that is achieved by choosing and using additives according to the invention. If desired, you also get the advantage that less of the long-chain esterification partner can be used.

Eksempel 2 Example 2

I følgende tabell oppføres resultater oppnådd ved måling av øvre hellepunkter (Inst. Pet. Method 15/67) på forskjellige restoljer. Den aktive bestanddel i det tilsatte additiv var en monobehenylester av maleinsyreanhydrid/C22_2g-alfa-olefin-kopolymer, fremstilt i henhold til fremstilling 1 og 4. The following table lists results obtained by measuring upper pour points (Inst. Pet. Method 15/67) on different residual oils. The active ingredient in the added additive was a monobehenyl ester of maleic anhydride/C22_2g-alpha-olefin copolymer, prepared according to Preparations 1 and 4.

Claims (6)

1. Flytende hydrokarbonsammensetning med nedsatt hellepunkt, karakterisert ved at den som hovedkomponent inneholder en flashdestillert brenselolje eller en råolje eller skiferolje, eller fortrinnsvis en restoljeholdig olje, og 0,0001 til 10%, fortrinnsvis 0,0005 til 0,5 vektprosent, på basis av brennstoffets eller oljens vekt, av et reaksjonsprodukt mellom a) en alkohol inneholdende minst 16, fortrinnsvis 20 til 26 C-atomer pr. molekyl og b) en kopolymer av komonomere omfattende (1) en etylenisk umettet dikarboksylsyre eller -anhydrid eller -derivat, og (2) minst étt alfa-olefin som inneholder minst 20 og fortrinnsvis 20 til 50 C-atomer pr. molekyl. ' 1. Liquid hydrocarbon composition with a reduced pour point, characterized in that it contains as the main component a flash-distilled fuel oil or a crude oil or shale oil, or preferably a residual oil-containing oil, and 0.0001 to 10%, preferably 0.0005 to 0.5% by weight, on a basis of the weight of the fuel or oil, of a reaction product between a) an alcohol containing at least 16, preferably 20 to 26 C atoms per molecule and b) a copolymer of comonomers comprising (1) an ethylenically unsaturated dicarboxylic acid or anhydride or derivative, and (2) at least one alpha-olefin containing at least 20 and preferably 20 to 50 C atoms per molecule. ' 2. Hydrokarbonsammensetning som angitt i krav 1, karakterisert ved at de komonomere (2) er minst ett alfa-olefin med 22 til 30, fortrinnsvis 22 til 28 C-atomer pr. molekyl.2. Hydrocarbon composition as stated in claim 1, characterized in that the comonomers (2) are at least one alpha-olefin with 22 to 30, preferably 22 to 28 C atoms per molecule. 3. Hydrokarbonsammensetning som angitt i krav 1 eller 2, karakterisert ved at den komonomere (1) er maleinsyre, fumarsyre eller fortrinnsvis maleinsyreanhydrid.3. Hydrocarbon composition as stated in claim 1 or 2, characterized in that the comonomer (1) is maleic acid, fumaric acid or preferably maleic anhydride. 4. Hydrokarbonsammensetning som angitt i et eller flere av de ovenstående krav, karakterisert ved at alkoholen er en alifatisk, i det vesentlige lineær monohydroksyalkohol, fortrinnsvis behenylalkohol.4. Hydrocarbon composition as stated in one or more of the above claims, characterized in that the alcohol is an aliphatic, essentially linear monohydroxy alcohol, preferably behenyl alcohol. 5. Hydrokarbonsammensetning som angitt i krav 4, karakterisert ved at reaksjonsproduktet er en behenylester, fortrinnsvis en monoester av maleinsyreanhydrid/C22_28~a-'-f a~°lef kopolymer.5. Hydrocarbon composition as stated in claim 4, characterized in that the reaction product is a behenyl ester, preferably a monoester of maleic anhydride/C22_28~a-'-f a~°lef copolymer. 6. Middel for nedsettelse av hellepunktet for en flytende hydrokarbonsammensetning ifølge krav 1, karakterisert ved at det består av et reaksjonsprodukt mellom a) en alkohol inneholdende minst 16, fortrinnsvis 20 - 26 C-atomer pr. molekyl, og b) en kopolymer av komonomerene omfattende (1) en etylenisk umettet dikarboksylsyre eller -anhydrid eller -derivat, og (2) minst ett alfa-olefin som inneholder minst 20 og fortrinnsvis 20 - 50 C-atomer pr. molekyl.6. Means for lowering the pour point of a liquid hydrocarbon composition according to claim 1, characterized in that it consists of a reaction product between a) an alcohol containing at least 16, preferably 20 - 26 C atoms per molecule, and b) a copolymer of the comonomers comprising (1) an ethylenically unsaturated dicarboxylic acid or anhydride or derivative, and (2) at least one alpha-olefin containing at least 20 and preferably 20-50 C atoms per molecule.
NO03853/70A 1969-10-14 1970-10-13 NO128873B (en)

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ES (1) ES384446A1 (en)
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US4151069A (en) * 1974-10-17 1979-04-24 Exxon Research & Engineering Co. Olefin-dicarboxylic anhydride copolymers and esters thereof are dewaxing aids
DE3340211T1 (en) * 1982-04-12 1984-04-05 Mitsubishi Chemical Industries Ltd., Tokyo Low temperature fluidity improver
FR2528066A1 (en) * 1982-06-04 1983-12-09 Inst Francais Du Petrole NITROGEN ADDITIVES FOR USE AS HYDROCARBON MOISTURE DISTILLATE DISORDER DISORDERS AND HYDROCARBON MEAL DISTILLATE COMPOSITIONS COMPRISING THE SAME
FR2535723A1 (en) * 1982-11-09 1984-05-11 Inst Francais Du Petrole NITROGEN ADDITIVES FOR USE AS HYDROCARBON MOISTURE DISTILLATE DISORDER DISORDERS AND HYDROCARBON MEAL DISTILLATE COMPOSITIONS COMPRISING THE SAME
US4654050A (en) * 1985-01-18 1987-03-31 The Lubrizol Corporation Esters of carboxy-containing interpolymers
GB8521393D0 (en) * 1985-08-28 1985-10-02 Exxon Chemical Patents Inc Middle distillate compositions
DE3742630A1 (en) * 1987-12-16 1989-06-29 Hoechst Ag POLYMER BLENDS FOR IMPROVING THE FLOWABILITY OF MINERAL OIL DISTILLATES IN THE COLD
DE19901803B4 (en) 1999-01-19 2005-04-07 Clariant Gmbh Copolymers and their use as an additive for improving the cold flow properties of middle distillates
FR2802940B1 (en) 1999-12-28 2003-11-07 Elf Antar France COMPOSITION OF MULTIFUNCTIONAL ADDITIVES FOR COLD OPERABILITY OF MEDIUM DISTILLATES
CN109535297B (en) * 2018-11-06 2021-03-30 江南大学 Copolymer with amido bond on side chain, preparation method and application thereof

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DE2050071A1 (en) 1971-04-29
JPS5015005B1 (en) 1975-06-02
CA959262A (en) 1974-12-17
FR2065425A5 (en) 1971-07-23
NL7015073A (en) 1971-04-16

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