NO177470B - Use of selected copolymer types of acrylic and / or methacrylic acid esters as flow enhancers in paraffin-rich petroleum and petroleum fractions - Google Patents
Use of selected copolymer types of acrylic and / or methacrylic acid esters as flow enhancers in paraffin-rich petroleum and petroleum fractions Download PDFInfo
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- NO177470B NO177470B NO890937A NO890937A NO177470B NO 177470 B NO177470 B NO 177470B NO 890937 A NO890937 A NO 890937A NO 890937 A NO890937 A NO 890937A NO 177470 B NO177470 B NO 177470B
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- Prior art keywords
- pour point
- maleic anhydride
- alcohol
- acrylic
- petroleum
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- 229920001577 copolymer Polymers 0.000 title claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 7
- 239000012188 paraffin wax Substances 0.000 title claims description 7
- 239000003208 petroleum Substances 0.000 title claims description 7
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 3
- 239000003623 enhancer Substances 0.000 title 1
- 239000010779 crude oil Substances 0.000 claims description 25
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- 238000007711 solidification Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- -1 acrylate ester Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- NVFYKZBOLSIHEI-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.O=C1OC(=O)C=C1 NVFYKZBOLSIHEI-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10L1/1963—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 mono-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
- C10L1/18—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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Description
Det er kjent at flytegenskapene for råoljer og/eller jordoljefraksjoner kan forbedres ved medanvendelse av begrensede mengder syntetiske flythjelpemidler. Oppgave for disse flyt-hjelpemidlene er som kjent å redusere den temperatur under hvilken i de flytende hydrokarbonblandinger de faste bestanddeler, spesielt høyere paraffiner eventuelt kombinasjoner med asfaltener eller andre tungtoppløselige bestanddeler, utkrystalliserer i slike mengder at flytevnene for hydro-karbonblandingen påvirkes ugunstig. Det her antydede temperaturområde fastslås ved i og for seg kjente metoder for bestemmelse av flytpunkt henholdsvis størkningspunkt. Hver råolje henholdsvis derav utvundne jordoljefraksjoner får på grunn av sin spesifikke sammensetning et egenflytpunkt som ved mange råolje dog ligger så lavt at det ikke har noen innflytelse ved transport og rørledningstransport. Det finnes imidlertid en hel rekke jordoljekvaliteter hvis størkningspunkt ligger over 10°C. Allerede her kan det være gunstig å gjennomføre medanvendelse av flythjelpemidler på basis av forskjellige syntetiske homopolymer- og/eller kopolymertyper. It is known that the flow properties of crude oils and/or petroleum fractions can be improved by co-using limited amounts of synthetic flow aids. The task of these flow aids is, as is well known, to reduce the temperature below which in the liquid hydrocarbon mixtures the solid components, especially higher paraffins or possibly combinations with asphaltenes or other poorly soluble components, crystallize in such quantities that the buoyancy of the hydrocarbon mixture is adversely affected. The temperature range indicated here is determined by methods known per se for determining the pour point or solidification point. Due to its specific composition, each crude oil or crude oil fractions extracted from it has an intrinsic pour point which, in the case of many crude oils, is so low that it has no influence during transport and pipeline transport. However, there is a whole range of crude oil qualities whose solidification point is above 10°C. Already here, it can be advantageous to carry out co-use of flow aids on the basis of different synthetic homopolymer and/or copolymer types.
Det foreligger en omfangsrik kjent teknikk i forbindelse med slike hjelpemidler som også leilighetsvis kalles paraffinin-hibitorer og som som regel fremstilles ved polymerisering av olefinisk umettede forbindelser som i det minste delvis inneholder ikke-forgrenede, mettede hydrokarbonkjeder med minst 18 karbonatomer. Det skal spesielt henvises til DE-AS 22 10 431 samt DE-OS 26 12 757, 22 64 328, 20 62 023, 23 30 232, 19 42 504 og 20 47 448. There is an extensive known technique in connection with such aids which are also occasionally called paraffinin inhibitors and which are usually produced by polymerization of olefinically unsaturated compounds which at least partially contain unbranched, saturated hydrocarbon chains with at least 18 carbon atoms. Particular reference should be made to DE-AS 22 10 431 and DE-OS 26 12 757, 22 64 328, 20 62 023, 23 30 232, 19 42 504 and 20 47 448.
Spesielle vanskeligheter opptrer i praksis når egenflytpunktet for råoljer henholdsvis jordoljefraksjoner som skal bearbeides, stiger til ekstremt høye verdier og som spesielt utgjør minst 25°C og derved kan ligge ved 30"C og derover. Jordoljematerialer av denne typen har allerede ved omgivel-sestemperatur en tendens til rask størkning. Hvis for eksempel pumping avbrytes kun i kort tid eller hvis det gjennomløpes vesentlige temperaturområder, for eksempel i havvannsområdet, ved transporten, kan den raske størkning av hydrokarbongodset føre til en ikke lengre pumpbar masse og dermed føre til blokkering av ledninger, pumper og lignende. Det hele vanskeliggjøres ved at det for på sikker måte å utelukke forstyrrelser av den nevnte type i praksis hyppig er nødvendig å redusere flytpunktet for oljene henholdsvis oljefraksjonene til verdier under 15 og spesielt til verdier under 12 eller sogar under 10°C. Det er selvfølgelig klart at det foreligger teknologiske vanskeligheter av en meget spesiell type når det for eksempel er spørsmål om å redusere egenflytpunktet til en råolje fra ca. 33°C til verdier klart under 10°C. Som ytterligere vanskelighet må man ta hensyn til at den enkle forhøyelse av tilsetningsmengden av et hvilket som helst flytpunktforbedringsmiddel generelt ikke fører til en tilsvarende forhøyet reduksjon av flytpunktet. Generelt må man kunne si at til nu ikke oppklarte inter-aksjoner mellom flythjelpemiddel og de størknede bestanddeler i råoljen skyldes en slags terskeleffekt med henblikk på det tilstrebede mål, hvorved den spesielle konstitusjon av flythjelpemidlet har avgjørende betydning for virkningen. Special difficulties arise in practice when the intrinsic pour point of crude oils or crude oil fractions to be processed rises to extremely high values, which in particular amount to at least 25°C and thereby can be at 30"C and above. Crude oil materials of this type already have at ambient temperature a tendency to rapid solidification. If, for example, pumping is only interrupted for a short time or if significant temperature ranges are passed through, for example in the seawater area, during transport, the rapid solidification of the hydrocarbon goods can lead to a mass that can no longer be pumped and thus lead to blockage of lines, pumps etc. The whole thing is made more difficult by the fact that, in order to reliably exclude disturbances of the aforementioned type, in practice it is often necessary to reduce the pour point of the oils or the oil fractions to values below 15 and especially to values below 12 or even below 10°C. It is of course clear that there are technological difficulties of a very special nature ial type when, for example, there is a question of reducing the intrinsic pour point of a crude oil from approx. 33°C to values clearly below 10°C. As a further difficulty, consideration must be given to the fact that the simple increase in the amount of addition of any pour point improver generally does not lead to a correspondingly increased reduction in the pour point. In general, one must be able to say that the hitherto unexplained interactions between the flow aid and the solidified components in the crude oil are due to a kind of threshold effect with regard to the intended goal, whereby the special constitution of the flow aid is of decisive importance for the effect.
I DE-PS 30 31 900 beskrives det blandingspolymerisater av n-akrylakrylater med minst 16 - C-atomer i alkoholresten og maleinsyreanhydrid i molforholdet n-alkylakrylat:maleinsyreanhydrid på 20:1 til 1:10. Forbindelser av denne type sies å skulle anvendes som krystalliseringsinhibitorer for paraffinholdige råoljer. Tallmessig viste eksempler angår anvendelser av tilsvarende kopolymerer i molforhold akrylsyre:maleinsyreanhydrid innen området 1:1 til 8:1. Overveiende anvendes derved råoljer med egenstørkningspunkter på under 20°C. En vurderingstabell beskjeftiger seg med india-råolje som, som kjent, er et spesielt paraffinrikt utgangsmateriale (forstyrrende paraffininnhold 15%) og som har et egenstørkningspunkt på 33°C. Den optimale virksomhet for det i denne publikasjon anvendte blandingspolymerisat med henblikk på størkningspunktsreduksjonen for dette utgangsmateriale ligger ved et molforhold akrylsyreester:maleinsyreanhydrid på 4:1. Det laveste her innstilte størkningspunkt ligger ved 12°C. Hvis maleinsyreanhydridandelen i kopolymeri-satet senkes ytterligere stiger størkningspunktet for den dermed behandlede indiråolje ved mengde lik tilsetning igjen (se til dette spesielt tabell 2 i henvisningen). DE-PS 30 31 900 describes mixed polymers of n-acrylic acrylates with at least 16 - C atoms in the alcohol residue and maleic anhydride in the molar ratio n-alkyl acrylate: maleic anhydride of 20:1 to 1:10. Compounds of this type are said to be used as crystallization inhibitors for paraffinic crude oils. Numerically shown examples relate to the use of corresponding copolymers in the molar ratio of acrylic acid: maleic anhydride within the range of 1:1 to 8:1. Crude oils with intrinsic solidification points below 20°C are mainly used. A rating table deals with India crude oil which, as is known, is a particularly paraffin-rich starting material (interfering paraffin content 15%) and which has an intrinsic solidification point of 33°C. The optimum activity for the mixed polymer used in this publication with a view to the solidification point reduction for this starting material lies at a molar ratio of acrylic acid ester: maleic anhydride of 4:1. The lowest solidification point set here is at 12°C. If the proportion of maleic anhydride in the copolymer is lowered further, the solidification point of the indira oil thus treated rises again with an equal amount of addition (see in particular table 2 in the reference).
Læren ifølge foreliggende oppfinnelse går i motsetning til dette ut fra den overraskende erkjennelse at en spesielt virkningsfull reduksjon av størkningstemperaturen, bestemt etter de kjente metoder, og/eller størkningspunktbestemmelse, kan oppnås ved utgangsmaterialer med høyt paraffininnhold og tilsvarende spesielt høye egenstørkningstemperaturer på effektiv måte når kopolymertyper av den sistnevnte type anvendes som flythjelpemidler idet de utmerker seg ved et ekstremt lavt innhold av maleinsyreanhydrid. Det har overraskende vist seg at utvalgte kopolymerisater med ekstremt lavt maleinsyreanhydridinnhold kan være spesielt godt egnet og nettopp virkningsfulle med henblikk på å senke grense-temperaturen for flytevnen av høyparaffinholdige råoljer henholdsvis tilsvarende råoljefraksjoner. The teaching according to the present invention is, in contrast, based on the surprising recognition that a particularly effective reduction of the solidification temperature, determined according to the known methods, and/or solidification point determination, can be achieved with starting materials with a high paraffin content and correspondingly particularly high self-solidification temperatures in an efficient manner when copolymer types of the latter type are used as flow aids as they are distinguished by an extremely low content of maleic anhydride. It has surprisingly been shown that selected copolymers with an extremely low maleic anhydride content can be particularly well suited and precisely effective with a view to lowering the limit temperature for the fluidity of highly paraffinic crude oils or corresponding crude oil fractions.
Gjenstand for foreliggende oppfinnelse er i henhold til dette anvendelsen av kopolymerer av akryl- og/eller metakryl-syreestere av høyere alkoholer henholdsvis alkoholsnitt med minst 16 C-atomer i alkoholresten og 0,5 til 2,5 vekt-# maleinsyreanhydrid (på vektbasis beregnet på kopolymervekten) som hellepunktsforbedrer i paraffinrike råoljer og/eller jordoljefraksjoner med inherente hellepunkt over 25° C for å redusere hellepunktet til verdier under 15°C og fortrinnsvis til under 10°C. The object of the present invention is, according to this, the use of copolymers of acrylic and/or methacrylic acid esters of higher alcohols, respectively alcohol ratios with at least 16 C atoms in the alcohol residue and 0.5 to 2.5 wt # of maleic anhydride (calculated on a weight basis on the copolymer weight) as a pour point improver in paraffin-rich crude oils and/or petroleum fractions with inherent pour points above 25°C to reduce the pour point to values below 15°C and preferably to below 10°C.
Spesielt egnet er for oppfinnelsens tanke kopolymerer av den innledningsvis nevnte art hvis innhold av maleinsyreanhydrid ligger innen området ca. 0,5 til 2,5 vekt-# og fortrinnsvis innen området ca. 1 til 2 vekt-#. Også her er alle data å forstå som vekt-56 av totalmonomeren • Innenfor rammen av oppfinnelsen ligger som antydet å innstille flytpunktet for de anvendte råoljer og/eller jordoljefraksjoner med utgangs-henholdsvis egenflytpunkt over 25<0>C og spesielt over 30 °C via tilsetning av den ifølge oppfinnelsen definerte flytforbedrer til verdier under 15 og fortrinnsvis under 10°C. I henhold til oppfinnelsen vil det således for eksempel være mulig, ved hjelp av tilsetning av konvensjonelle mengder flytpunktfor-bedrer i henhold til oppfinnelsen, å komme til flytpunkt for ekstremt paraffinrike utgangsstoffer innen området ca. 0 til 8°C. Dermed kan man sikre forstyrrelsesfri behandling også av slike råoljer henholdsvis råoljefraksjoner under vanlige driftsbetingelser. I tillegg til dette sikres det at man kan benytte undervannsledninger, fordelere og lignende utstyr uten vanskelighet. Particularly suitable for the purposes of the invention are copolymers of the type mentioned at the outset whose content of maleic anhydride is within the range of approx. 0.5 to 2.5 weight-# and preferably within the range of approx. 1 to 2 weight #. Here, too, all data is to be understood as weight-56 of the total monomer • Within the scope of the invention, as indicated, is to set the pour point for the used crude oils and/or petroleum fractions with an initial, respectively, intrinsic pour point above 25<0>C and especially above 30 °C via addition of the flow improver defined according to the invention to values below 15 and preferably below 10°C. According to the invention, it will thus be possible, for example, by adding conventional amounts of pour point improver according to the invention, to reach the pour point for extremely paraffin-rich starting materials within the range of approx. 0 to 8°C. In this way, disturbance-free processing can also be ensured of such crude oils or crude oil fractions under normal operating conditions. In addition to this, it is ensured that underwater lines, distributors and similar equipment can be used without difficulty.
Spesielt egner seg for oppfinnelsens lære små mengder maleinsyreanhydridholdige kopolymerer på basis av - akrylsyreester. Den videre spesielt foretrukne akrylsyreester inneholder sammenligningsvis langkjedede alkoholrester som overveiende kan være n-alkylrester og oppvise foretrukne kjedelengder i området Ci8-24- Åndelsvis kan man anvende alkoholer med høyere karbontall, spesielt opp til ca. C3Q og/eller alkoholer med lavere karbontall til C-^, samtidig. Spesielt fremmes oppløsningsoppførselen for kopolymerisatene i vanlige oppløsningsmidler, for eksempel toluen eller lignende, via anvendelse av tilsvarende alkoholsnitt ved fremstilling av akrylsyreesteren og den derpå følgende kopolymerisering med maleinsyreanhydrid. Particularly suitable for the teachings of the invention are small amounts of maleic anhydride-containing copolymers based on acrylic acid ester. The further particularly preferred acrylic acid ester contains, by comparison, long-chain alcohol residues which may predominantly be n-alkyl residues and exhibit preferred chain lengths in the range C18-24. In spirit, alcohols with higher carbon numbers can be used, especially up to approx. C3Q and/or alcohols with lower carbon numbers to C-^, at the same time. In particular, the dissolution behavior of the copolymers in common solvents, for example toluene or the like, is promoted via the use of a corresponding alcohol ratio in the preparation of the acrylic acid ester and the subsequent copolymerization with maleic anhydride.
Det har videre vist seg at ved medanvendelse av kun små mengder maleinsyreanhydrid som komonomer innenfor oppfinnelsens lære når det gjelder flytpunktforbedring, kan det oppnås spesielt virksomme kopolymerer når det foreligger sammenligningsvis høye innhold av alkoholrester med minst 22 C-atomer i akrylat- henholdsvis metakrylatkomponenten. Således kan det innenfor oppfinnelsens ramme være hensiktsmessig å anvende alkohol snitt for fremstilling av akrylatkomponenter hvis innhold av C22_alkohol i det minste utgjør ca. 35 vekt-# og spesielt minst ca. 45 vekt-#. Spesielt gode flytpunktfor-bedrere oppnås når disse langkjedede alkoholkomponenter i de for fremstilling av (met )akrylatkomponentene anvendte alkoholsnitt ligger over 50 vekt-#. De her angitte vekt-# tall gjelder innholdet av C22 alkohol og eventuelt høyere alkoholer i blandingen som anvendes for fremstilling av akrylat- henholdsvis metakrylatkomponentene. It has also been shown that by co-using only small amounts of maleic anhydride as comonomer within the teachings of the invention in terms of pour point improvement, particularly effective copolymers can be obtained when there is a comparatively high content of alcohol residues with at least 22 C atoms in the acrylate or methacrylate component. Thus, within the scope of the invention, it may be appropriate to use alcohol fractions for the production of acrylate components whose C22_alcohol content is at least approx. 35 weight # and especially at least approx. 45 weight #. Particularly good pour point improvers are obtained when these long-chain alcohol components in the alcohol ratio used for the production of the (meth)acrylate components are above 50% by weight. The weight # figures given here apply to the content of C22 alcohol and possibly higher alcohols in the mixture used for the production of the acrylate and methacrylate components.
Anvendelseskonsentrasjonen for oppfinnelsens flytpunktfor-bedrere ligger innenfor det konvensjonelle område og utgjør for eksempel 20 til 1.000 ppm hvorved mengder innen området 100 til 500 ppm foretrekkes. De flytpunktforbedrende midler benyttes derved hensiktsmessig i egnede oppløsningsmidler. Enkeltheter til dette samt for fremstilling av kopolymerisater finnes i den kjente teknikk, for eksempel i det innledningsvis nevnte DE-PS 30 31 900. The application concentration for the pour point improvers of the invention lies within the conventional range and amounts to, for example, 20 to 1,000 ppm, whereby quantities within the range of 100 to 500 ppm are preferred. The pour point improvers are therefore used appropriately in suitable solvents. Details for this as well as for the production of copolymers can be found in the known technique, for example in the initially mentioned DE-PS 30 31 900.
De for fremstilling av akrylatkomponenten anvendte alkoholer eller alkoholsnitt kan være av nativ eller syntetisk opprinn-else. Alkoholsnitt med en overveiende andel av komponenter med minst 22 C-atomer, samtidig imidlertid også mindre mengder alkoholkomponenter innen området Ci6-20» er det foretrukne utgangsmateriale. I en spesiell utførelsesform av oppfinnelsen blir slike utvalgte akrylater henholdsvis metakrylater kopolymerisert med maleinsyreanhydrid i slike mengdeforhold at molforholdet alkyl-akrylatet henholdsvis-metakrylatrmaleinsyreanhydrid er større enn 20:1. The alcohols or alcohol cuts used for the production of the acrylate component can be of native or synthetic origin. Alcohol cuts with a predominant proportion of components with at least 22 C atoms, but at the same time also smaller amounts of alcohol components in the range Ci6-20" is the preferred starting material. In a particular embodiment of the invention, such selected acrylates or methacrylates are copolymerized with maleic anhydride in such quantities that the molar ratio alkyl-acrylate or methacrylate-maleic anhydride is greater than 20:1.
Eksempler Examples
For fremstilling av maleinsyreanhydrid kopolymerisatene anvender man de to akrylatesterblandinger A og B som skiller seg ved C-kjedefordeling til de i ethvert tilfelle anvendte fettalkoholblandinger ved akrylsyreforestringen. De to akrylattyper karakteriseres derved som følger: For the production of the maleic anhydride copolymers, the two acrylate ester mixtures A and B are used, which differ in C chain distribution from the fatty alcohol mixtures used in each case in the acrylic acid esterification. The two acrylate types are thereby characterized as follows:
For fremstilling av akrylat/MAH-kopolymerer anvendes det to fremgangsmåtetyper, nemlig en sats- og en kontinuerlig type. For the production of acrylate/MAH copolymers, two types of process are used, namely a batch type and a continuous type.
Forsøksg. iennomføring ved satsmetoden trial implementation by the rate method
Monomerer, initiatorer og oppløsningsmidler veies inn i en trehalskolbe. Monomers, initiators and solvents are weighed into a three-necked flask.
Med et røreromdreiningstall på 70 omdr./minutt blir ansatsen evakuert 10 ganger 1 minutt og dette undertrykk hver gang avlastet med 99,999#-ig nitrogne. Med en omdreiningshast-ighet på 50 omdreininger/minutt og under en lett N£-strøm blir det hele oppvarmet til 90°C og holdt ved denne temperatur. Under hele reaksjonen arbeider man under inerte betingelser. Reaksjonsstart viser seg ved en temperaturstig-ning til 93 til 9b°C. Det hele holdes i 3 timer ved 90 + rc. Etter denne reaksjonsperiode avkjøler man i løpet av 45 minutter til romtemperatur og produktet helles av. With a stirrer speed of 70 rpm, the mixture is evacuated 10 times for 1 minute and this negative pressure is each time relieved with 99.999#-ig nitrogen. With a rotational speed of 50 revolutions/minute and under a light N£ current, the whole is heated to 90°C and held at this temperature. During the entire reaction, one works under inert conditions. The reaction starts when the temperature rises to 93 to 9b°C. The whole thing is kept for 3 hours at 90 + rc. After this reaction period, it is cooled to room temperature within 45 minutes and the product is poured off.
Som oppløsningsmiddel benytter man her og i de etterfølgende fremstillingsmetoder toluen. Den anvendte polymeriserings-initiator er dibenzoylperoksyd eller azoisobutyronitril som angitt nedenfor. Blandingsforholdet oppløsningsmiddel:monom-erblanding er 1:1 på vektbasis. Toluene is used as a solvent here and in the subsequent production methods. The polymerization initiator used is dibenzoyl peroxide or azoisobutyronitrile as indicated below. The solvent:monomer mixture ratio is 1:1 by weight.
Forsøksg. iennomf ør ing ved tilløpsmetoden trial implementation by the accrual method
Monomerene oppløses i de ønskede blandingsforhold ved 45 til 50°C i toluen og oppløsningen avkjøles deretter til 25 °C. Også initiatoren anvendes oppløst i toluen. Ca. 20% av den pr. sats bestemte monomeroppløsning forelegges i en reaktor. Reaktoren spyles tre ganger med nitrogen og oppvarmes under en lett N2 strøm under omrøring til 90°C. Initiatoroppløs-ningen blir nu tilsatt på en slik måte at den totale doseringstid er 2,5 timer. The monomers are dissolved in the desired mixing ratios at 45 to 50°C in toluene and the solution is then cooled to 25°C. The initiator is also used dissolved in toluene. About. 20% of it per Rate-determined monomer solution is placed in a reactor. The reactor is flushed three times with nitrogen and heated under a light N2 stream with stirring to 90°C. The initiator solution is now added in such a way that the total dosing time is 2.5 hours.
Ca. 20 minutter etter start av initiatortilsetningen skjer det en temperaturforhøyelse. Temperaturen holdes ved avkjøling av reaksjonskappen ved 90 + 3°C. 30 minutter etter begynt initiatortilsetning blir den gjenværende monomeroppløsning dosert til reaktoren på en slik måte at den totale doseringstid utgjør 2 timer. Under hele reaksjonstiden holdes temperaturen ved 90 + 3°C. Deretter blir reaksjonsblandingen holdt i ytterligere 6 minutter ved den samme temperatur. Deretter blir reaksjonsproduktet avkjølt og helt av ved 30° C. I den følgende tabell 2 er oppfinnelsens eksempler 1-3 sammenfattet. Derved tilordnes det til hvert eksempel typen av anvendt akrylmonomer A henholdsvis B samt ^-andelen på vektbasis av maleinsyrean-hydridet i monomerblandingen for fremstilling av det hellepunktssenkende middel. I eksemplene 1 og 2 er det hellepunktsforbedrende middel fremstilt i henhold til en satsmetode og i eksemplene 3 til 10 i henhold til en tilløpsmetode. About. 20 minutes after the start of the initiator addition, an increase in temperature occurs. The temperature is maintained by cooling the reaction jacket at 90 + 3°C. 30 minutes after initiator addition has begun, the remaining monomer solution is dosed to the reactor in such a way that the total dosing time amounts to 2 hours. During the entire reaction time, the temperature is kept at 90 + 3°C. The reaction mixture is then kept for a further 6 minutes at the same temperature. The reaction product is then cooled and poured off at 30° C. Examples 1-3 of the invention are summarized in the following table 2. Thereby, the type of acrylic monomer A and B used as well as the proportion by weight of the maleic anhydride in the monomer mixture for the production of the pour point lowering agent are assigned to each example. In examples 1 and 2, the pour point improver is prepared according to a batch method and in examples 3 to 10 according to a batch method.
I eksemplene 1 og 7 anvendes det som initiator azoisobutyronitril, i alle andre eksempler anvendes dibenzoylperoksyd. In examples 1 and 7, azoisobutyronitrile is used as initiator, in all other examples dibenzoyl peroxide is used.
Tabell 2 viser til slutt den spesifikke viskositet for den i hvert tilfelle fremstilte kopolymeroppløsning. Viskositets-målingen skjer derved ved hjelp av et Ubbelohde-viskosimeter med kapillar I med diameter 0,63 mm. De målte toluenopp-løsninger er derved 3#-ig i toluen. Målingen skjer ved 20° C etter en temperaturutgjevning på 10 minutter. Table 2 finally shows the specific viscosity of the copolymer solution prepared in each case. The viscosity measurement is thereby carried out using an Ubbelohde viscometer with capillary I with a diameter of 0.63 mm. The measured toluene solutions are therefore 3#-ig in toluene. The measurement takes place at 20° C after a temperature equalization of 10 minutes.
Tabell 2 inneholder til slutt hellepunktsverdiene som er oppnådd ved tilsetning av oppfinnelsens hellepunktsforbedrende middel til et "India-Crude" (Bombay-råolje) i henhold til den følgende arbeidsprosedyre. Table 2 finally contains the pour point values obtained by adding the pour point improver of the invention to an "India-Crude" (Bombay crude oil) according to the following working procedure.
Bestemmelse av hellepunktene Determination of the pour points
Hellepunktet ble bestemt som følger under henvisning til ASTM D 97-66 henholdsvis DIN 51597: 25 g Bombay-råolje ble sammen med 800 ppm av en 50 vekt-# oppløsning av hellepunktforbedreren gitt til en lukket beholder i 15 minutter og holdt ved 50°C og i regelmessige intervaller rystet kraftig 5 ganger. Den således behandlede råolje ble hurtig omfylt til en sylinderformig glassbeholder med en indre diameter på 27 mm og denne umiddelbart lukkede beholder hengt tilstrekkelig dypt i et vannbad med temperatur +36°C. The pour point was determined as follows with reference to ASTM D 97-66 and DIN 51597 respectively: 25 g of Bombay crude oil together with 800 ppm of a 50 wt # solution of the pour point improver was given to a closed container for 15 minutes and kept at 50°C and at regular intervals shook violently 5 times. The thus treated crude oil was quickly refilled into a cylindrical glass container with an inner diameter of 27 mm and this immediately closed container hung sufficiently deep in a water bath with a temperature of +36°C.
Etter 39 minutter ble glasset skråstilt noe og man undersøkte hvorvidt innholdet var flytende. Det hele ble så trinnvis avkjølt med 3°C/trinn og prøveprosedyren fullført hver gang. Til den temperatur ved hvilken innholdet ikke lenger var flytende, ikke engang ved en helling av glasset på 90°, ble det lagt 3°C og denne temperatur er angitt som hellepunktet. After 39 minutes, the glass was tilted slightly and it was examined whether the contents were liquid. The whole was then stepwise cooled at 3°C/step and the test procedure completed each time. To the temperature at which the contents were no longer liquid, not even when the glass was tilted at 90°, 3°C was added and this temperature is designated as the pour point.
Hellepunktet for ubehandlede Bombay-råoljer ligger i henhold til denne metode ved ca. 30°C. According to this method, the pour point for untreated Bombay crude oils is approx. 30°C.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3807394A DE3807394A1 (en) | 1988-03-07 | 1988-03-07 | USE OF SELECTED COPOLYMER TYPES OF ACRYLIC AND / OR METHACRYLIC ACID ESTERS AS FLOW-IMPROVERS IN PARAFFIN-LIKE PETROLEUM AND PETROLEUM FRACTIONS (I) |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO890937D0 NO890937D0 (en) | 1989-03-06 |
| NO890937L NO890937L (en) | 1989-09-08 |
| NO177470B true NO177470B (en) | 1995-06-12 |
| NO177470C NO177470C (en) | 1995-09-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO890937A NO177470C (en) | 1988-03-07 | 1989-03-06 | Use of selected copolymer types of acrylic and / or methacrylic acid esters as flow enhancers in paraffin-rich petroleum and petroleum fractions |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0332000B1 (en) |
| JP (1) | JPH01290892A (en) |
| AR (1) | AR247930A1 (en) |
| AU (1) | AU610700B2 (en) |
| BR (1) | BR8901035A (en) |
| CA (1) | CA1334013C (en) |
| DE (2) | DE3807394A1 (en) |
| DK (1) | DK110689A (en) |
| MX (1) | MX172301B (en) |
| NO (1) | NO177470C (en) |
| TR (1) | TR23834A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3830913A1 (en) * | 1988-09-10 | 1990-03-15 | Henkel Kgaa | NEW WAFER EMULSION SCOPOLYMERISES, ESPECIALLY A WATER AND OIL DEFINITIVE FORM FOR IMPROVING FLOW PROPERTIES AND POINT POINT LIGHTING OF PETROLEUM AND PETROLEUM FRACTIONS, AND THEIR USE |
| FR2710652B1 (en) * | 1993-09-30 | 1995-12-01 | Elf Antar France | Composition of cold operability additives for middle distillates. |
| CN104710560B (en) * | 2013-12-13 | 2017-06-06 | 中国石油天然气集团公司 | A kind of dicyclopentadiene and Long Chain Alkyl Acrylate polymer pour point depressant for crude oil |
| RU2541680C1 (en) * | 2014-03-21 | 2015-02-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Inhibitor of asphaltresinparaffin sediments |
| WO2017153462A1 (en) | 2016-03-10 | 2017-09-14 | Basf Se | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
| US20190062660A1 (en) * | 2016-04-21 | 2019-02-28 | Universitaet Hamburg | Crude oil composition comprising an additive for improving the flow properties of paraffin-containing crude oil |
| LU93040B1 (en) * | 2016-04-21 | 2017-10-27 | Univ Hamburg | Additive for improving the flow properties of paraffinic crude oils |
| CN109114426B (en) * | 2017-06-26 | 2020-09-04 | 中国石油天然气集团公司 | Composition for crude oil pour point depressant, preparation method and application |
| SG11202002161XA (en) | 2017-09-11 | 2020-04-29 | Basf Corp | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1068401A (en) * | 1965-02-08 | 1967-05-10 | Exxon Research Engineering Co | Improved motor fuel composition |
| US3904385A (en) * | 1972-05-08 | 1975-09-09 | Texaco Inc | Polyacrylates and waxy residual fuel compositions thereof |
| DE3031900C2 (en) * | 1980-08-23 | 1983-06-09 | Chemische Fabriek Servo B.V., 7491 Delden | Copolymers of n-alkyl acrylates and maleic anhydride and their use as crystallization inhibitors for crude oils containing paraffin |
| FR2566288B1 (en) * | 1984-06-21 | 1991-10-18 | Elf Aquitaine | POLYMERIC ADDITIVES FOR USE INHIBITING THE DEPOSITION OF PARAFFINS IN RAW OILS |
-
1988
- 1988-03-07 DE DE3807394A patent/DE3807394A1/en not_active Withdrawn
-
1989
- 1989-02-27 DE DE58909795T patent/DE58909795D1/en not_active Expired - Lifetime
- 1989-02-27 EP EP89103383A patent/EP0332000B1/en not_active Expired - Lifetime
- 1989-03-03 TR TR89/0216A patent/TR23834A/en unknown
- 1989-03-03 MX MX015136A patent/MX172301B/en unknown
- 1989-03-06 BR BR898901035A patent/BR8901035A/en not_active Application Discontinuation
- 1989-03-06 AU AU31024/89A patent/AU610700B2/en not_active Ceased
- 1989-03-06 NO NO890937A patent/NO177470C/en unknown
- 1989-03-06 JP JP1053610A patent/JPH01290892A/en active Pending
- 1989-03-07 CA CA000592933A patent/CA1334013C/en not_active Expired - Fee Related
- 1989-03-07 DK DK110689A patent/DK110689A/en not_active Application Discontinuation
- 1989-03-07 AR AR89313350A patent/AR247930A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| AU3102489A (en) | 1989-09-07 |
| MX172301B (en) | 1993-12-13 |
| BR8901035A (en) | 1989-10-24 |
| NO177470C (en) | 1995-09-20 |
| AR247930A1 (en) | 1995-04-28 |
| EP0332000B1 (en) | 1997-05-02 |
| DE3807394A1 (en) | 1989-09-21 |
| DK110689A (en) | 1989-09-08 |
| DE58909795D1 (en) | 1997-06-05 |
| EP0332000A2 (en) | 1989-09-13 |
| CA1334013C (en) | 1995-01-17 |
| NO890937L (en) | 1989-09-08 |
| NO890937D0 (en) | 1989-03-06 |
| EP0332000A3 (en) | 1990-04-18 |
| AU610700B2 (en) | 1991-05-23 |
| TR23834A (en) | 1990-09-25 |
| JPH01290892A (en) | 1989-11-22 |
| DK110689D0 (en) | 1989-03-07 |
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