EP0332002A2 - Use of selected acrylic and/or methacrylic acid ester copolymers as flow enhancers in paraffin-rich mineral oils and mineral-oil fractions (II) - Google Patents
Use of selected acrylic and/or methacrylic acid ester copolymers as flow enhancers in paraffin-rich mineral oils and mineral-oil fractions (II) Download PDFInfo
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- EP0332002A2 EP0332002A2 EP89103385A EP89103385A EP0332002A2 EP 0332002 A2 EP0332002 A2 EP 0332002A2 EP 89103385 A EP89103385 A EP 89103385A EP 89103385 A EP89103385 A EP 89103385A EP 0332002 A2 EP0332002 A2 EP 0332002A2
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Classifications
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
- C10L10/16—Pour-point depressants
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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
- C10L1/18—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/927—Well cleaning fluid
- Y10S507/929—Cleaning organic contaminant
- Y10S507/93—Organic contaminant is asphaltic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/927—Well cleaning fluid
- Y10S507/929—Cleaning organic contaminant
- Y10S507/931—Organic contaminant is paraffinic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0391—Affecting flow by the addition of material or energy
Definitions
- auxiliaries which are also referred to as paraffin inhibitors are and are usually prepared by polymerization of olefinically unsaturated compounds which contain at least partially unbranched saturated hydrocarbon chains with at least 18 carbon atoms.
- DE-PS 30 31 900 describes copolymers of n-alkyl acrylates with at least 16 carbon atoms in the alcohol residue and maleic anhydride with molar ratios of n-alkyl acrylate to maleic anhydride from 20 1 to 1:10. Compounds of this type are said to be used as crystallization inhibitors for paraffin-containing crude oils. Examples shown numerically relate to the use of corresponding copolymers in the molar ratio of the acrylic acid ester to maleic anhydride in the range from 1: 1 to 8: 1. Crude oils with intrinsic pour points below 20 ° C. are predominantly used.
- a table of values deals with India crude oil, which is known to be a particularly paraffin-rich starting material (disruptive paraffin content 15%) and has an intrinsic pour point of 33 ° C.
- the optimum effectiveness of the copolymers used in this publication with regard to lowering the pour point on this starting material is at the molar ratio of acrylic acid ester / maleic anhydride of 4: 1.
- the lowest pour points set here are at 12 ° C. If the proportion of maleic anhydride in the copolymer is further reduced, then the pour points of the India crude oil thus added rise again with the addition of the same amount (cf. in particular Table 2 of the cited literature reference).
- the teaching of the present invention is based on the knowledge that a particularly effective lowering of the solidification temperatures - determined by the known methods of pour point and / or pour point determination lung - and an effective improvement in flow behavior can be obtained even in the temperature range just above the lowered pour point if the copolymer types described below in detail from acrylic and / or methacrylic acid esters of higher alcohols and free acrylic acid and / or methacrylic acid in limited amounts as comonomers be used for the purpose of lowering the pour point.
- the invention accordingly relates to the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue and not more than 20% by weight of free acrylic acid and / or methacrylic acid as additives for paraffins and if appropriate, crude oils and petroleum fractions containing asphaltenes to lower their pour point or solidification point and to improve the flow properties, in particular in the temperature range just above the solidification point.
- copolymers of the type mentioned contain, together with the acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts, about 0.5 to 15% by weight of the free acids mentioned, copolymers of the type mentioned having free acid contents in the range of about 1 to 10% by weight may be particularly suitable.
- the most important copolymers of the type used according to the invention contain acrylic acid and / or methacrylic acid as comonomers in the copolymers shown above in amounts of about 1.5 to 5.0% by weight. All these percentages by weight relate in each case to the copolymer weight.
- the additives which lower the pour point and improve the flow properties of the treated oils or oil fractions can be used with advantage in general for crude oils or petroleum fractions of any origin. Their use is particularly helpful in the problems described at the outset of the paraffin-rich crude oils and / or petroleum fractions with their own pour points above 20 ° C. and in particular above 25 ° C.
- pour point improvers according to the invention in only limited quantities, it is possible to use the pour points even with these feedstocks lower to values below 15 ° C and preferably to values below 10 ° C. This is possible even if the starting or self-pour points of the oils or oil fractions are at 30 ° C or above.
- pour point improvers it is thus possible, by adding conventional amounts of the pour point improvers, to obtain pour points in the range from about 0 to 8 ° C. even with extremely paraffin-rich starting materials. This ensures trouble-free handling of these crude oils and oil fractions under normal everyday conditions. In particular, it is ensured that lines, distributors and the like which are guided under water can be operated without problems.
- the weight percentages given here relate to the content of C22 alcohol - and possibly higher alcohols - in the alcohol mixture which has been used for the production of the acrylate components.
- the application concentration of the pour point improvers according to the invention is in the conventional range and is for example 20 to 1000 ppm, with amounts in the range of 100 to 500 ppm being preferred.
- the pour point improvers are expediently used in suitable solvents. Details on this and the preparation of the copolymers can be found in the relevant prior art, for example in DE-PS 30 31 900 already cited.
- the alcohols or alcohol cuts used for the production of the acrylate components can be of native or synthetic origin. Alcohol cuts with a predominant proportion of components with at least 22 carbon atoms, but at the same time also minor amounts of alcohol components in the range C16 to C20, are the preferred feedstocks.
- the two acrylate ester mixtures A and B are used, which differ in the C chain distribution of the fatty alcohol mixture used for the acrylic acid esterification.
- the two types of acrylate are characterized as follows: Table 1 C chain distribution of fatty alcohol /% C16 C18 C20 C22 Acrylate A 16.3 22.9 10.7 46.9 Acrylate B 1.5 8.6 15.2 68.8
- Two types of processes are used to produce the acrylate / acrylic acid copolymers, the batch process and the feed process.
- the monomers, initiator and solvent are weighed into a three-necked flask.
- the batch is evacuated for 10 ⁇ 1 min and the vacuum is released again with 99.999% nitrogen.
- the batch is heated to 90 ° C. and kept at this temperature.
- the entire reaction is carried out under inert conditions.
- the start of the reaction manifests itself in a temperature rise to 93 to 96 ° C.
- the mixture is kept at 90 ° C ⁇ 1 ° C for 3 h. After this time, the mixture is cooled to room temperature within 45 minutes and the product is filled.
- Toluene is used as the solvent here and in the subsequent feed process.
- the polymerization initiator used is dibenzoyl peroxide or azoisobutyronitrile as indicated below.
- the mixing ratio of solvent to monomer mixture is 1: 1 (parts by weight).
- the monomers are dissolved in toluene in the desired mixing ratio at 45 to 50 ° C. and the solution is then cooled to 25 ° C.
- the initiator is also used in solution in toluene. About 20% of those determined per approach Monomer solution is placed in a reactor. The reactor is flushed three times with nitrogen and heated to 90 ° C. while stirring under a slight stream of N 2. The initiator solution is now metered in so that the total metering time is 2.5 hours.
- a temperature increase occurs 20 minutes after the initiator has been added.
- the temperature is kept at 90 ⁇ 3 ° C by cooling the reactor jacket.
- the remaining monomer solution is metered into the reactor such that the total metering time is 2 hours.
- the temperature is kept at 90 ⁇ 3 ° C throughout the reaction time.
- the reaction mixture is then kept at the same temperature for a further 60 min.
- the reaction product is then cooled and filled at 30 ° C.
- Examples 1 to 12 according to the invention are summarized in Table 2 below.
- the type of acrylate monomers A or B used is assigned to the respective example and the percentage (% by weight) of acrylic acid in the monomer mixture for the preparation of the pour point depressant is given.
- the flow improver was produced by the batch process and in examples 2 to 12 by the feed process.
- Table 2 finally shows the specific viscosity of the copolymer solutions prepared in each case.
- the viscose The actuality is measured using an Ubbelohde viscometer, capillary I, ⁇ 0.63 mm.
- the measured toluene solutions are 3% solutions in toluene. The measurement is carried out at 20 ° C after a temperature adjustment of 10 min.
- Table 2 contains the pour point values which are used when adding the pour point according to the invention. improved to an India crude (Bombay crude oil) according to the following work instructions.
- the pour point was determined in accordance with ASTM D 97-66 and DIN 51597 as follows:
- the pour point of the untreated Bombay crude oil is 30 ° C according to this determination method.
- the yield point was 99 Nm ⁇ 2 for the material according to the invention and 1990 Nm ⁇ 2 for the branded product.
- the technical advantage of the flow improver according to the invention can be seen from this.
- the pump pressure that has to be applied to start up a pipeline filled with cooled crude oil is 48 times after 2 hours and still 20 times after 20 hours of working according to the teaching of the invention in the market product that was also tested.
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- Combustion & Propulsion (AREA)
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- Liquid Carbonaceous Fuels (AREA)
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Abstract
Description
Es ist bekannt, die Fließeigenschaften von Rohölen und/oder Erdölfraktionen durch Mitverwendung beschränkter Mengen synthetischer Fließhilfsmittel zu verbessern. Aufgabe dieser Fließhilfsmittel ist bekanntlich die Absenkung der jeweiligen Temperatur unterhalb derer im flüssigen Kohlenwasserstoffgemisch Festbestandteile - insbesondere höhere Paraffine gegebenenfalls in Kombination mit Asphaltenen oder anderen schwer löslichen Bestandteilen - in solchen Mengen auskristallisieren, daß die Fließfähigkeit der Kohlenwasserstoffgemische nachhaltig beeinträchtigt wird. Der hier angesprochene Temperaturbereich wird durch die bekannten Methoden der Bestimmung von Fließpunkt bzw. Stockpunkt ermittelt. Jedem Rohöl bzw. den daraus gewonnenen Erdölfraktionen kommt aufgrund seiner spezifischen Zusammensetzung ein Eigenfließpunkt zu, der bei vielen Rohölen jedoch so niedrig liegt, daß keine Beeinträchtigung bei der Förderung und beim Pipelinetransport eintritt. Es gibt aber auch eine ganze Reihe von Erdölqualitäten, deren Stockpunkt oberhalb von 10 °C liegt. Schon hier kann für die Praxis die Mitverwendung von Fließhilfsmitteln auf Basis unterschiedlicher synthetischer Homopolymer- und/oder Copolymertypen ratsam sein.It is known to improve the flow properties of crude oils and / or petroleum fractions by using limited amounts of synthetic flow aids. As is known, the task of these flow aids is to lower the respective temperature below those in the liquid hydrocarbon mixture of solid constituents - in particular higher paraffins, if appropriate in combination with asphaltenes or other poorly soluble constituents - in such amounts that the flowability of the hydrocarbon mixtures is permanently impaired. The temperature range mentioned here is determined by the known methods of determining the pour point or pour point. Due to its specific composition, each crude oil or the petroleum fractions obtained from it has its own pour point, which, however, is so low for many crude oils that there is no impairment in production and pipeline transport. But there is also a whole range of petroleum qualities with a pour point above 10 ° C. In practice, the use of flow aids based on different synthetic homopolymer and / or copolymer types can be advisable.
Es besteht ein umfangreicher Stand der Technik zu solchen Hilfsmitteln, die auch als Paraffininhibitoren bezeichnet werden und in der Regel durch Polymerisation von olefinisch ungesättigten Verbindungen, die wenigstens anteilweise unverzweigte gesättigte Kohlenwasserstoffketten mit mindestens 18 C-Atomen enthalten, hergestellt werden. Verwiesen wird beispielsweise auf die DE-AS 22 10 431 sowie die DE-OSen 26 12 757, 22 64 328, 20 62 023, 23 30 232, 19 42 504 und 20 47 448.There is extensive prior art for such auxiliaries, which are also referred to as paraffin inhibitors are and are usually prepared by polymerization of olefinically unsaturated compounds which contain at least partially unbranched saturated hydrocarbon chains with at least 18 carbon atoms. Reference is made, for example, to DE-AS 22 10 431 and DE-OSs 26 12 757, 22 64 328, 20 62 023, 23 30 232, 19 42 504 and 20 47 448.
Besondere Schwierigkeiten treten für die Praxis dann auf, wenn der Eigenfließpunkt des Rohöls bzw. der zu bearbeitenden Erdölfraktion extrem hohe Werte erreicht, die insbesondere wenigstens 25 °C ausmachen und dabei 30 °C und darüber liegen können. Erdölmaterialien dieser Art neigen schon bei Umgebungstemperatur zu rascher Verfestigung. Werden beispielsweise Pumpvorgänge auch nur kurzfristig unterbrochen oder werden im Transport Temperaturbereiche - beispielsweise durch Leitungen im Meerwasserbereich mit verhältinsmäßig niedrigen Temperaturen durchschritten, so tritt die rasche Verfestigung des Kohlenwasserstoffguts zu einer nicht mehr pumpfähigen Masse und damit die Blockade von Leitungen, Pumpen und dergleichen ein. Erschwert wird der Sachverhalt dadurch, daß zum sicheren Ausschluß von Störungen der geschilderten Art von der Praxis häufig gefordert wird, die Fließpunkte der Öle bzw. Ölfraktionen auf Werte unterhalb 15 °C und insbesondere auf Werte unter 12 °C oder gar unter 10 °C abzusenken. Es leuchtet sofort ein, daß technologische Schwierigkeiten ganz besonderer Art dann vorliegen, wenn es beispielsweise gilt, einen Eigenfließpunkt des Rohöls von etwa 33 °C auf Werte deutlich unterhalb 10 °C abzusenken. Als zusätzliche Schwierigkeit ist dabei zu berücksichtigen, daß die einfache Erhöhung der Zusatzmenge beliebiger Fließpunktsverbesserer im allgemeinen nicht zu entsprechend erhöhter Abnahme des Fließpunktes führt. Im einzelnen nicht aufgeklärte Interaktionen zwischen Fließhilfsmittel und den sich verfe stigenden Bestandteilen des Rohöls sind wohl etwa im Sinne eines Thresh-hold-Effektes für das angestrebte Ziel verantwortlich zu machen, wobei der bestimmten Konstitution des Fließhilfsmittels entscheidende Bedeutung für seine Wirksamkeit zukommt.In practice, particular difficulties arise when the intrinsic pour point of the crude oil or the petroleum fraction to be processed reaches extremely high values, which in particular can be at least 25 ° C and can be 30 ° C and above. Petroleum materials of this type tend to solidify rapidly even at ambient temperature. If, for example, pumping processes are interrupted even for a short time or if temperature ranges are exceeded in transport - for example through pipes in the seawater area with relatively low temperatures, the rapid solidification of the hydrocarbon material to a mass that is no longer pumpable and thus the blocking of pipes, pumps and the like occurs. The situation is made more difficult by the fact that, in order to reliably rule out malfunctions of the type described, practice is often required to lower the pour points of the oils or oil fractions to values below 15 ° C. and in particular to values below 12 ° C. or even below 10 ° C. . It immediately makes sense that there are very special technological difficulties when, for example, it is necessary to lower the crude oil's own pour point from around 33 ° C to values well below 10 ° C. An additional difficulty to be taken into account here is that simply increasing the amount of any pour point improver generally does not result in a correspondingly increased decrease in the pour point. In particular, unexplained interactions between flow aids and the The increasing constituents of the crude oil are probably responsible for the desired goal in the sense of a thresh-hold effect, whereby the specific constitution of the flow aid is of decisive importance for its effectiveness.
In der DE-PS 30 31 900 werden Mischpolymerisate aus n-Alkylacrylaten mit mindestens 16 C-Atomen im Alkoholrest und Maleinsäureanhydrid mit Molverhältnissen von n-Alkylacrylat zu Maleinsäureanhydrid von 20 1 bis 1 : 10 beschrieben. Verbindungen dieser Art sollen als Kristallisationsinhibitoren für paraffinhaltige Rohöle eingesetzt werden. Zahlenmäßig dargestellte Beispiele betreffen die Verwendung entsprechender Copolymere im Molverhältnis des Acrylsäureesters zum Maleinsäureanhydrid im Bereich von 1 : 1 bis 8 : 1. Überwiegend werden dabei Rohöle mit Eigenstockpunkten unterhalb 20 °C eingesetzt. Eine Wertetabelle beschäftigt sich mit dem India-Rohöl, das bekanntlich ein besonders paraffinreiches Ausgangsmaterial ist (störender Paraffingehalt 15 %) und einen Eigenstockpunkt von 33 °C besitzt. Die optimale Wirksamkeit der in dieser Druckschrift verwendeten Mischpolymerisate bezüglich der Stockpunkterniedrigung an diesem Ausgangsmaterial liegt beim Molverhältnis Acrylsäureester/Maleinsäureanhydrid von 4 : 1. Die niedrigsten hier eingestellten Stockpunkte liegen bei 12 °C. Wird der Maleinsäureanhydrid-Anteil im Copolymerisat weiter abgesenkt, dann steigen die Stockpunkte des damit versetzten India-Rohöls bei mengengleicher Zugabe wieder an (vgl. hierzu insbesondere die Tabelle 2 der genannten Literaturstelle).DE-PS 30 31 900 describes copolymers of n-alkyl acrylates with at least 16 carbon atoms in the alcohol residue and maleic anhydride with molar ratios of n-alkyl acrylate to maleic anhydride from 20 1 to 1:10. Compounds of this type are said to be used as crystallization inhibitors for paraffin-containing crude oils. Examples shown numerically relate to the use of corresponding copolymers in the molar ratio of the acrylic acid ester to maleic anhydride in the range from 1: 1 to 8: 1. Crude oils with intrinsic pour points below 20 ° C. are predominantly used. A table of values deals with India crude oil, which is known to be a particularly paraffin-rich starting material (disruptive paraffin content 15%) and has an intrinsic pour point of 33 ° C. The optimum effectiveness of the copolymers used in this publication with regard to lowering the pour point on this starting material is at the molar ratio of acrylic acid ester / maleic anhydride of 4: 1. The lowest pour points set here are at 12 ° C. If the proportion of maleic anhydride in the copolymer is further reduced, then the pour points of the India crude oil thus added rise again with the addition of the same amount (cf. in particular Table 2 of the cited literature reference).
Die Lehre der vorliegenden Erfindung geht demgegenüber von der Erkenntnis aus, daß eine besonders wirkungsvolle Absenkung der Verfestigungstemperaturen - bestimmt nach den bekannten Methoden der Fließpunkt- und/oder Stockpunktermitt lung - sowie eine wirkungsvolle Verbesserung des Fließverhaltens auch gerade im Temperaturbereich dicht oberhalb der abgesenkten Fließpunkte erhalten werden können, wenn die im nachfolgenden im einzelnen geschilderten Copolymertypen aus Acryl- und/oder Methacrylsäureestern höherer Alkohole und freier Acrylsäure und/oder Methacrylsäure in beschränkten Mengen als Comonomere für den Zweck der Fließpunktabsenkung eingesetzt werden.The teaching of the present invention, on the other hand, is based on the knowledge that a particularly effective lowering of the solidification temperatures - determined by the known methods of pour point and / or pour point determination lung - and an effective improvement in flow behavior can be obtained even in the temperature range just above the lowered pour point if the copolymer types described below in detail from acrylic and / or methacrylic acid esters of higher alcohols and free acrylic acid and / or methacrylic acid in limited amounts as comonomers be used for the purpose of lowering the pour point.
Gegenstand der Erfindung ist dementsprechend die Verwendung von Copolymeren aus Acryl- und/oder Methacrylsäureestern höherer Alkohole bzw. Alkoholschnitte mit wenigstens 16 C-Atomen im Alkoholrest und nicht mehr als 20 Gew.-% an freier Acrylsäure und/oder Methacrylsäure als Zuschlagmittel für Paraffine sowie gegebenenfalls Asphaltene enthaltende Rohöle und Erdölfraktionen zur Absenkung deren Fließ- bzw. Erstarrungspunkt und zur Verbesserung der Fließeigenschaften insbesondere im Temperaturbereich kurz oberhalb des Erstarrungspunktes.The invention accordingly relates to the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue and not more than 20% by weight of free acrylic acid and / or methacrylic acid as additives for paraffins and if appropriate, crude oils and petroleum fractions containing asphaltenes to lower their pour point or solidification point and to improve the flow properties, in particular in the temperature range just above the solidification point.
Besonders geeignete Copolymere der genannten Art enthalten zusammen mit den Acryl- und/oder Methacrylsäureestern höherer Alkohole bzw. Alkoholschnitte etwa 0,5 bis 15 Gew.-% der genannten freien Säuren, wobei Copolymere der angegebenen Art mit Gehalten an freier Säure im Bereich von etwa 1 bis 10 Gew.-% besonders geeignet sein können. Die wichtigsten Copolymere der erfindungsgemäß eingesetzten Art enthalten Acrylsäure und/oder Methacrylsäure als Comonomere im zuvor dargestellten Copolymeren in Mengen von etwa 1,5 bis 5,0 Gew.-%. Dabei beziehen sich alle diese Gew.-%-Angaben jeweils auf das Copolymergewicht.Particularly suitable copolymers of the type mentioned contain, together with the acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts, about 0.5 to 15% by weight of the free acids mentioned, copolymers of the type mentioned having free acid contents in the range of about 1 to 10% by weight may be particularly suitable. The most important copolymers of the type used according to the invention contain acrylic acid and / or methacrylic acid as comonomers in the copolymers shown above in amounts of about 1.5 to 5.0% by weight. All these percentages by weight relate in each case to the copolymer weight.
Die den Fließpunkt absenkenden und die Fließeigenschaften der behandelten Öle bzw. Ölfraktionen verbessernden Zusatzstoffe der Erfindung können ganz allgemein bei Rohölen bzw. Erdölfraktionen beliebigen Ursprungs mit Vorteil verwendet werden. Besonders hilfreich ist ihr Einsatz in den eingangs geschilderten Problemfällen der paraffinreichen Rohöle und/oder Erdölfraktionen mit Eigenfließpunkten oberhalb 20 °C und insbesondere oberhalb 25 ° C. Durch die Verwendung der erfindungsgemäßen Fließpunktsverbesserer in nur beschränkten Mengen wird es möglich, auch bei diesen Einsatzmaterialien die Fließpunkte auf Werte unterhalb 15 ° C und bevorzugt auf Werte unter 10 ° C abzusenken. Das ist selbst dann möglich, wenn die Ausgangs- bzw. Eigenfließpunkte der Öle bzw. Ölfraktionen bei 30 ° C oder auch darüber liegen. Erfindungsgemäß wird es damit möglich, durch Zugabe konventioneller Mengen der Fließpunktsverbesserer auch bei extrem paraffinreichen Ausgangsmaterialien auf Fließpunkte im Bereich von etwa 0 bis 8 ° C zu kommen. Damit ist die störungsfreie Handhabung auch dieser Rohöle bzw. Ölfraktionen unter den normalen Alltagsbedingungen gewährleistet. Insbesondere ist sichergestellt, daß unter Wasser geführte Leitungen, Verteiler und dergleichen störungsfrei betrieben werden können.The additives which lower the pour point and improve the flow properties of the treated oils or oil fractions The invention can be used with advantage in general for crude oils or petroleum fractions of any origin. Their use is particularly helpful in the problems described at the outset of the paraffin-rich crude oils and / or petroleum fractions with their own pour points above 20 ° C. and in particular above 25 ° C. By using the pour point improvers according to the invention in only limited quantities, it is possible to use the pour points even with these feedstocks lower to values below 15 ° C and preferably to values below 10 ° C. This is possible even if the starting or self-pour points of the oils or oil fractions are at 30 ° C or above. According to the invention, it is thus possible, by adding conventional amounts of the pour point improvers, to obtain pour points in the range from about 0 to 8 ° C. even with extremely paraffin-rich starting materials. This ensures trouble-free handling of these crude oils and oil fractions under normal everyday conditions. In particular, it is ensured that lines, distributors and the like which are guided under water can be operated without problems.
Besonders geeignet sind für die Lehre der Erfindung geringe Mengen an Acrylsäure und/oder Methacrylsäure enthaltende Copolymere auf Basis von Estern dieser Säuren, die vergleichsweise langkettige Alkoholreste mit bevorzugten Kettenlängen im Bereich von C₁₈ bis C₂₄ aufweisen. Bei diesen Alkoholen bzw. Alkoholresten handelt es sich vorzugsweise überwiegend um entsprechende Verbindungen mit n-Alkylresten. Anteilsweise können Alkohole mit höherer Kohlenstoffzahl, insbesondere bis etwa C₃₀ und/oder Alkohole mit niedrigerer Kohlenstoffzahl bis etwa C₁₆ mitverwendet werden. Insbesondere das Lösungsverhalten der Copolymerisate in üblichen Lösungsmitteln, bei spielsweise Toluol und dergleichen, wird durch den Einsatz von entsprechenden Alkoholschnitten bei der Herstellung der Acryl- bzw. Methacrylsäureester und deren nachfolgende Copolymerisation mit den entsprechenden freien Säuren gefördert.Small quantities of copolymers containing acrylic acid and / or methacrylic acid based on esters of these acids, which have comparatively long-chain alcohol residues with preferred chain lengths in the range from C₁₈ to C₂₄, are particularly suitable for the teaching of the invention. These alcohols or alcohol residues are preferably predominantly corresponding compounds with n-alkyl residues. Proportions of alcohols with a higher carbon number, in particular up to about C₃₀ and / or alcohols with a lower carbon number up to about C₁₆ can also be used. In particular, the dissolution behavior of the copolymers in conventional solvents for example toluene and the like, is promoted by the use of appropriate alcohol cuts in the preparation of the acrylic or methacrylic acid esters and their subsequent copolymerization with the corresponding free acids.
Besondere Bedeutung kommt Fließverbesserern der geschilderten Art zu, die als freie Säure ausschließlich oder überwiegend Acrylsäure enthalten. Ebenso kommt den Estern der Acrylsäure als Comonomerbestandteil besondere Bedeutung im Sinne des erfindungsgemäßen Handelns zu.Flow improvers of the type described, which contain exclusively or predominantly acrylic acid as the free acid, are of particular importance. Likewise, the esters of acrylic acid as a comonomer component are of particular importance in the sense of the action according to the invention.
Es hat sich weiterhin gezeigt, daß bei der Mitverwendung von Acrylsäure und/oder Methacrylsäure als Comonomere in den erfindungsgemäß eingesetzten Fließpunktverbesserern dann besonders wirkungsvolle Copolymere erhalten werden, wenn vergleichsweise hohe Gehalte an Alkoholresten mit wenigstens 22 C-Atomen in der Acrylat- bzw. Methacrylat-Komponente vorliegen. So kann es im Sinne der Erfindung zweckmäßig sein, Alkoholschnitte für die Herstellung der Acrylatkomponente (n) einzusetzen, deren Gehalt an C₂₂-Alkohol wenigstens etwa 25 Gew.-%, vorzugsweise wenigstens etwa 35 Gew.-% und insbesondere wenigstens etwa 45 Gew.-% ausmacht. Besonders gute Fließpunktverbesserer werden dann erhalten, wenn diese langkettigen Alkoholkomponenten in den zur Herstellung der (Meth)-Acrylatkomponente eingesetzten Alkoholschnitten oberhalb von 50 Gew.-% liegen.It has also been shown that when acrylic acid and / or methacrylic acid are used as comonomers in the pour point improvers used according to the invention, particularly effective copolymers are obtained if comparatively high contents of alcohol residues with at least 22 carbon atoms in the acrylate or methacrylate Component. So it can be useful in the context of the invention to use alcohol cuts for the production of the acrylate component (s), the content of C₂₂ alcohol at least about 25 wt .-%, preferably at least about 35 wt .-% and in particular at least about 45 wt. -% makes up. Particularly good pour point improvers are obtained if these long-chain alcohol components in the alcohol cuts used to produce the (meth) acrylate component are above 50% by weight.
Die hier angegebenen Gewichtsprozent-Zahlen beziehen sich auf den Gehalt an C₂₂-Alkohol - und gegebenenfalls höheren Alkoholen - im Alkoholgemisch, das für die Herstellung der Acrylatkomponenten verwendet worden ist.The weight percentages given here relate to the content of C₂₂ alcohol - and possibly higher alcohols - in the alcohol mixture which has been used for the production of the acrylate components.
Die Anwendungskonzentration der erfindungsgemäßen Fließpunktverbesserer liegt im konventionellen Bereich und beträgt bei spielsweise 20 bis 1 000 ppm, wobei Mengen im Bereich von 100 bis 500 ppm bevorzugt werden. Die Fließpunktverbesserer werden dabei zweckmäßigerweise in geeigneten Lösungsmitteln eingesetzt. Einzelheiten hierzu sowie zur Herstellung der Copolymerisate finden sich im einschlägigen Stand der Technik, beispielsweise in der bereits zitierten DE-PS 30 31 900.The application concentration of the pour point improvers according to the invention is in the conventional range and is for example 20 to 1000 ppm, with amounts in the range of 100 to 500 ppm being preferred. The pour point improvers are expediently used in suitable solvents. Details on this and the preparation of the copolymers can be found in the relevant prior art, for example in DE-PS 30 31 900 already cited.
Die für die Herstellung der Acrylatkomponenten eingesetzten Alkohole oder Alkoholschnitte können nativen oder synthetischen Ursprungs sein. Alkoholschnitte mit einem überwiegenden Anteil an Komponenten mit wenigstens 22 C-Atomen, gleichzeitig aber auch untergeordneten Mengen an Alkoholkomponenten des Bereichs C₁₆ bis C₂₀, sind die bevorzugten Einsatzmaterialien.The alcohols or alcohol cuts used for the production of the acrylate components can be of native or synthetic origin. Alcohol cuts with a predominant proportion of components with at least 22 carbon atoms, but at the same time also minor amounts of alcohol components in the range C₁₆ to C₂₀, are the preferred feedstocks.
Zur Herstellung der Acrylsäure-Copolymerisate werden die beiden Acrylatestergemische A und B eingesetzt, die sich durch die C-Kettenverteilung des jeweils zur Acrylsäureveresterung eingesetzten Fettalkoholgemisches unterscheiden. Die beiden Acrylattypen kennzeichnen sich dabei wie folgt:
Zur Herstellung der Acrylat/Acrylsäure-Copolymeren werden zwei Verfahrenstypen eingesetzt, das Batch-Verfahren und das Zulaufverfahren.Two types of processes are used to produce the acrylate / acrylic acid copolymers, the batch process and the feed process.
Die Monomeren, Initiator und Lösungsmittel werden in einen Dreihalskolben eingewogen.The monomers, initiator and solvent are weighed into a three-necked flask.
Bei einer Rührerdrehzahl von 70 Upm wird der Ansatz 10 x 1 min lang evakuiert und das Vakuum jeweils mit 99,999 %igem Stickstoff wieder aufgehoben. Bei einer Rührerdrehzahl von 50 Upm und unter leichtem N₂-Strom wird der Ansatz auf 90 °C erwärmt und bei dieser Temperatur gehalten. Während der gesamten Reaktion wird unter Inertbedingungen gearbeitet. Das Anspringen der Reaktion äußert sich in einem Temperaturanstieg auf 93 bis 96 °C. Der Ansatz wird 3 h bei 90 °C ± 1 °C gehalten. Nach dieser Zeit wird innerhalb von 45 min auf Raumtemperatur abgekühlt und das Produkt abgefüllt.At a stirrer speed of 70 rpm, the batch is evacuated for 10 × 1 min and the vacuum is released again with 99.999% nitrogen. At a stirrer speed of 50 rpm and under a slight stream of N₂, the batch is heated to 90 ° C. and kept at this temperature. The entire reaction is carried out under inert conditions. The start of the reaction manifests itself in a temperature rise to 93 to 96 ° C. The mixture is kept at 90 ° C ± 1 ° C for 3 h. After this time, the mixture is cooled to room temperature within 45 minutes and the product is filled.
Als Lösungsmittel wird hier und im nachfolgenden Zulaufverfahren Toluol eingesetzt. Der eingesetzte Polymerisationsinitiator ist Dibenzoylperoxid oder Azoisobutyronitril wie nachstehend noch angegeben. Das Mischungsverhältnis von Lösungsmittel zu Monomerengemisch beträgt l : 1 (Gew.-Teile).Toluene is used as the solvent here and in the subsequent feed process. The polymerization initiator used is dibenzoyl peroxide or azoisobutyronitrile as indicated below. The mixing ratio of solvent to monomer mixture is 1: 1 (parts by weight).
Die Monomeren werden im jeweils gewünschten Mischungsverhältnis bei 45 bis 50 °C in Toluol gelöst und die Lösung anschließend auf 25 °C abgekühlt. Auch der Initiator wird in Toluol gelöst eingesetzt. Etwa 20 % der pro Ansatz bestimmten Monomerlösung wird in einem Reaktor vorgelegt. Der Reaktor wird dreimal mit Stickstoff gespült und unter leichtem N₂-Strom unter Rühren auf 90 °C erwärmt. Die Initiatorlösung wird jetzt so zudosiert, daß die Gesamtdosierzeit 2,5 h beträgt.The monomers are dissolved in toluene in the desired mixing ratio at 45 to 50 ° C. and the solution is then cooled to 25 ° C. The initiator is also used in solution in toluene. About 20% of those determined per approach Monomer solution is placed in a reactor. The reactor is flushed three times with nitrogen and heated to 90 ° C. while stirring under a slight stream of N 2. The initiator solution is now metered in so that the total metering time is 2.5 hours.
Ca. 20 min nach Beginn der Initiatorzugabe tritt eine Temperaturerhöhung auf. Die Temperatur wird durch Kühlen des Reaktormantels bei 90 ± 3 °C gehalten.Approx. A temperature increase occurs 20 minutes after the initiator has been added. The temperature is kept at 90 ± 3 ° C by cooling the reactor jacket.
30 min nach Beginn der Initiatorzugabe wird die restliche Monomerlösung so in den Reaktor dosiert, daß die Gesamtdosierzeit 2 h beträgt. Während der gesamten Reaktionszeit wird die Temperatur bei 90 ± 3 °C gehalten. Nachfolgend wird das Reaktionsgemisch weitere 60 min bei der gleichen Temperatur gehalten. Anschließend wird das Reaktionsprodukt gekühlt und bei 30 °C abgefüllt.30 minutes after the initiator has been added, the remaining monomer solution is metered into the reactor such that the total metering time is 2 hours. The temperature is kept at 90 ± 3 ° C throughout the reaction time. The reaction mixture is then kept at the same temperature for a further 60 min. The reaction product is then cooled and filled at 30 ° C.
In der nachfolgenden Tabelle 2 sind die erfindungsgemäßen Beispiele 1 bis 12 zusammengefaßt. Dabei wird dem jeweiligen Beispiel der Typ des eingesetzten Acrylatmonomeren A bzw. B zugeordnet und der Prozentgehalt (Gew.-%) der Acrylsäure im Monomerengemisch zur Herstellung des Fließpunkterniedrigers angegeben. In Beispiel 1 ist dabei der Fließverbesserer nach dem Batch-Verfahren und in den Beispielen 2 bis 12 nach dem Zulaufverfahren hergestellt worden.Examples 1 to 12 according to the invention are summarized in Table 2 below. The type of acrylate monomers A or B used is assigned to the respective example and the percentage (% by weight) of acrylic acid in the monomer mixture for the preparation of the pour point depressant is given. In example 1, the flow improver was produced by the batch process and in examples 2 to 12 by the feed process.
In den Beispielen 1 und 7 ist als Initiator Azoisobutyronitril, in allen anderen Beispielen als Initiator Dibenzoylperoxid verwendet worden.In examples 1 and 7, azoisobutyronitrile was used as the initiator, and dibenzoyl peroxide was used as the initiator in all other examples.
Die Tabelle 2 zeigt schließlich die spezifische Viskosität der jeweils hergestellten Copolymerlösungen. Die Viskosi tätsmessung erfolgt dabei mit einem Ubbelohde-Viskosimeter, Kapillare I, ⌀ 0,63 mm. Die vermessenen Toluollösungen sind dabei 3 %ige Lösungen in Toluol. Die Messung wird bei 20 °C nach einer Temperaturangleichung von 10 min durchgeführt.Table 2 finally shows the specific viscosity of the copolymer solutions prepared in each case. The viscose The actuality is measured using an Ubbelohde viscometer, capillary I, ⌀ 0.63 mm. The measured toluene solutions are 3% solutions in toluene. The measurement is carried out at 20 ° C after a temperature adjustment of 10 min.
Die Tabelle 2 enthält schließlich die Fließpunktwerte (Pourpoint), die bei der Zugabe der erfindungsgemäßen Fließpunkt-. verbesserer zu einem India-Crude (Bombay-Rohöl) gemäß der nachfolgenden Arbeitsanweisung erhalten worden sind.Finally, Table 2 contains the pour point values which are used when adding the pour point according to the invention. improved to an India crude (Bombay crude oil) according to the following work instructions.
Der Pourpoint wurde in Anlehnung an ASTM D 97-66 bzw. DIN 51597 wie folgt bestimmt:The pour point was determined in accordance with ASTM D 97-66 and DIN 51597 as follows:
25,0 g Bombay-Rohöl wurden zusammen mit 800 ppm der 50-gewichtsprozentigen Lösung des Fließverbesserers in einem geschlossenen Gefäß 15 min lang auf 50 °C gehalten und dabei 5mal in regelmäßigen Abständen kräftig geschüttelt. Das so gedopte Rohöl wurde rasch in ein zylinderförmiges Glasgefäß mit einem Innendurchmesser von 27 mm umgefüllt und dieses sogleich verschlossene Gefäß ausreichend tief in ein Wasserbad von + 36 °C gehängt.25.0 g of Bombay crude oil, together with 800 ppm of the 50% strength by weight solution of the flow improver, were kept in a closed vessel at 50 ° C. for 15 minutes and vigorously shaken 5 times at regular intervals. The crude oil doped in this way was quickly poured into a cylindrical glass vessel with an inside diameter of 27 mm and this immediately sealed vessel was hung sufficiently deep in a water bath at + 36 ° C.
Nach 30 min wurde das Glas leicht zur Seite geneigt und beobachtet, ob der Inhalt fließend war. Die Probe wurde nun schrittweise um je 3 °C gekühlt und die Prüfprozedur jedesmal vollzogen. Zur Temperatur, bei der der Inhalt auch bei Neigung des Prüfglases um 90 °C nicht mehr floß, wurden 3 °C addiert und diese Temperatur als Pourpoint festgelegt.After 30 minutes the glass was tilted slightly to the side and observed whether the contents were flowing. The sample was then gradually cooled by 3 ° C and the test procedure was carried out each time. 3 ° C was added to the temperature at which the contents no longer flowed, even when the test glass was inclined by 90 ° C, and this temperature was defined as the pour point.
Der Pourpoint des unbehandelten Bombay-Rohöls liegt nach dieser Bestimmungsmethode bei 30 °C.
In einer weiteren Untersuchung wird beim Einsatz des Fließpunktverbesserers gemäß Beispiel 6 die Bestimmung der Fließgrenze mit Hilfe des Rotationsviskosimeters CS 100 der Firma Carri-Med Ltd. vorgenommen. In gleicher Weise wird die entsprechende Wirkung eines handelsüblichen Markenproduktes auf Basis von Copolymerisaten langkettiger Acrylate und Pyridin bestimmt. Im einzelnen gilt dabei für diese Versuche das folgende:In a further investigation, when using the pour point improver according to Example 6, the determination of the yield point is carried out using the CS 100 rotary viscometer from Carri-Med Ltd. performed. The corresponding effect of a commercially available branded product based on copolymers of long-chain acrylates and pyridine is determined in the same way. The following applies in detail to these experiments:
10.0 g Bombay Rohöl, das mit a) 300 ppm des 50 %igen Fließverbesserers gemäß Beispiel 6 und in einer zweiten Probe mit b) 300 ppm eines 50 %igen bekannten und in der Praxis eingesetzten Fließverbesserers gedopt worden war, wurden 2 Stunden auf 6 °C gekühlt und sodann die Fließgrenze mit folgendem Ergebnis bestimmt:
Wurden die gedopten Rohöle statt 2 Stunden nun 72 Stunden auf 6 °C gehalten, betrug die Fließgrenze beim erfindungsgemäßen Material 99 N · m⁻² und beim Markenprodukt 1990 N · m⁻².If the doped crude oils were held at 6 ° C for 72 hours instead of 2 hours, the yield point was 99 Nm · 2 for the material according to the invention and 1990 Nm · 2 for the branded product.
Daraus ist der technische Vorteil des erfindungsgemäßen Fließverbesserers zu ersehen. Der Pumpendruck, der zum Anfahren einer mit ausgekühltem Rohöl gefüllten Pipeline aufgebracht werden muß, beträgt bei dem ebenfalls geprüften Marktprodukt nach 2 Stunden das 48-fache und nach 72 Stunden Kühlzeit immer noch das 20-fache des Arbeitens nach der Lehre der Erfindung.The technical advantage of the flow improver according to the invention can be seen from this. The pump pressure that has to be applied to start up a pipeline filled with cooled crude oil is 48 times after 2 hours and still 20 times after 20 hours of working according to the teaching of the invention in the market product that was also tested.
Claims (6)
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DE3807395A DE3807395A1 (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 (II) |
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US3735770A (en) * | 1972-02-09 | 1973-05-29 | Gulf Research Development Co | Method for increasing the mobility of waxy crude oils |
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-
1988
- 1988-03-07 DE DE3807395A patent/DE3807395A1/en not_active Withdrawn
-
1989
- 1989-02-27 DE DE8989103385T patent/DE58901132D1/en not_active Expired - Lifetime
- 1989-02-27 EP EP89103385A patent/EP0332002B2/en not_active Expired - Lifetime
- 1989-03-03 TR TR89/0217A patent/TR24478A/en unknown
- 1989-03-03 MX MX015137A patent/MX171036B/en unknown
- 1989-03-06 BR BR898901034A patent/BR8901034A/en not_active Application Discontinuation
- 1989-03-06 AU AU31025/89A patent/AU611265B2/en not_active Ceased
- 1989-03-06 NO NO890938A patent/NO176413C/en unknown
- 1989-03-06 JP JP1053609A patent/JPH01287393A/en active Pending
- 1989-03-07 US US07/320,122 patent/US5039432A/en not_active Expired - Lifetime
- 1989-03-07 DK DK110789A patent/DK110789A/en not_active Application Discontinuation
- 1989-03-07 CA CA000592935A patent/CA1327538C/en not_active Expired - Fee Related
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FR1258027A (en) * | 1959-05-28 | 1961-04-07 | Shell Int Research | Organic liquids with increased electrical conductivity |
DE2264328A1 (en) * | 1972-05-08 | 1973-11-29 | Texaco Development Corp | POLY (N-ALKYL ACRYLATE) AND ITS USE AS A STOCK POINT LOWER IN A HEAVY PETROLEUM FRACTION |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2982872A1 (en) * | 2011-11-22 | 2013-05-24 | Univ Sud Toulon Var | POLY (N-ALKYL ACRYLATE) POLYMERS AND THEIR USE AS OIL FLOW POINT SIZERS |
WO2013076424A1 (en) * | 2011-11-22 | 2013-05-30 | Universite Du Sud Toulon-Var | Poly(n-alkyl acrylate) polymers and use thereof as oil pour point depressants |
WO2021228701A1 (en) * | 2020-05-11 | 2021-11-18 | Croda International Plc | Paraffin inhibitor composition, method and use |
Also Published As
Publication number | Publication date |
---|---|
EP0332002A3 (en) | 1990-03-28 |
NO890938L (en) | 1989-09-08 |
NO890938D0 (en) | 1989-03-06 |
EP0332002B2 (en) | 1997-05-02 |
DE58901132D1 (en) | 1992-05-21 |
MX171036B (en) | 1993-09-27 |
NO176413B (en) | 1994-12-19 |
TR24478A (en) | 1991-10-11 |
NO176413C (en) | 1995-03-29 |
JPH01287393A (en) | 1989-11-20 |
AU611265B2 (en) | 1991-06-06 |
US5039432A (en) | 1991-08-13 |
BR8901034A (en) | 1989-10-24 |
CA1327538C (en) | 1994-03-08 |
DK110789A (en) | 1989-09-08 |
AU3102589A (en) | 1989-09-07 |
DE3807395A1 (en) | 1989-09-21 |
EP0332002B1 (en) | 1992-04-15 |
DK110789D0 (en) | 1989-03-07 |
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