EP0436151B1 - Distillat moyen de pétrole stable au froid contenant des copolymères comme dispersants de paraffine - Google Patents

Distillat moyen de pétrole stable au froid contenant des copolymères comme dispersants de paraffine Download PDF

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EP0436151B1
EP0436151B1 EP90123728A EP90123728A EP0436151B1 EP 0436151 B1 EP0436151 B1 EP 0436151B1 EP 90123728 A EP90123728 A EP 90123728A EP 90123728 A EP90123728 A EP 90123728A EP 0436151 B1 EP0436151 B1 EP 0436151B1
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copolymers
middle distillate
ppm
ethylene
polymerization
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EP0436151A1 (fr
EP0436151B2 (fr
Inventor
Knut Dr. Oppenlaender
Heinrich Dr. Hartmann
Walter Denzinger
Brigitte Dr. Wegner
Klaus Dr. Barthold
Erich Dr. Schwartz
Egon Buettner
Hans-Jürgen Raubenheimer
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BASF SE
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BASF SE
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • the invention relates to low-temperature petroleum middle distillates containing low molecular weight polymers with copolymerized monoethylenically unsaturated dicarboxylic acids which are reacted with unbranched, secondary fatty amines and have improved cold flowability and better dispersion of the separated wax crystals.
  • Middle distillates such as gas oils, diesel oils or heating oils, which are obtained from petroleum by distillation, have different paraffin contents depending on the origin of the crude oil.
  • solid paraffins are excreted (cloud point or cloud point, CP).
  • cloud point or cloud point, CP cloud point
  • the platelet-shaped n-paraffin crystals form a "house of cards” and the middle distillate stops, although the majority of the middle distillate is still liquid.
  • the fluidity of the petroleum distillate fuels is significantly impaired by the unusual n-paraffins in the temperature region between the cloud point and pour point or pour point.
  • the paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar problems occur with heating oils.
  • suitable additives can be used to modify the crystal growth of the paraffins in the petroleum middle distillate fuels.
  • Good-acting additives on the one hand prevent middle distillates from forming such house of cards structures and, at temperatures a few degrees Celsius below the temperature at which the first wax crystals crystallize, already become solid and, on the other hand, they form fine, well-crystallized, separate wax crystals that pass through filters in motor vehicles and heating systems or at least form a filter cake permeable to the liquid part of the middle distillates, so that trouble-free operation is ensured.
  • a disadvantage of the additives mentioned is that the failed wax crystals, owing to their higher density than the liquid part, tend to settle more and more on the bottom of the container during storage. This creates a homogeneous low-paraffin phase in the upper part of the container and a two-phase paraffin-rich layer on the bottom. Since both in vehicle tanks and in storage or delivery tanks of mineral oil dealers, the middle distillate is mostly removed a little above the bottom of the container, there is a risk that the high concentration of solid paraffins will lead to blockages of filters and metering devices. This danger increases the further the storage temperature falls below the paraffin separation temperature, since the amount of paraffin excreted is a function of the temperature and increases with decreasing temperature.
  • the paraffin crystal modifiers are polymers which change the crystal growth of the n-paraffins through co-crystallization (interaction) and improve the flow properties of the middle distillate at low temperatures.
  • the effectiveness of the flow improver is expressed indirectly according to DIN 51428 by measuring the "Cold Filters Plugging Point” (CFPP).
  • ethylene copolymers especially copolymers of ethylene and unsaturated esters
  • DE-A-2 531 234 the addition of dialkyl diamides or monoalkylimides of e.g. Styrene / maleic acid amide copolymers recommended as stabilizers in mineral oils, i.e. the carboxyl groups of the maleic anhydride radical are completely reacted with amines, so that there are no free carboxyl groups.
  • dialkyl diamides or monoalkylimides e.g. Styrene / maleic acid amide copolymers recommended as stabilizers in mineral oils, i.e. the carboxyl groups of the maleic anhydride radical are completely reacted with amines, so that there are no free carboxyl groups.
  • reaction products of monoamines with maleic anhydride polymers to give the corresponding imides are also described, wherein when using less than one mole of amine per mole of maleic anhydride unit, any remaining carboxyl groups are neutralized.
  • dialkylamines are also mentioned as reactants in the general description in the cited patent specification, there is no concrete information about a reaction with a secondary amine. Rather, there is always talk of imide to be formed, the formation of which is only possible with a primary amine. Finally, the reaction product should not contain any free acid groups; these are converted into metal salts by neutralization.
  • radicals of the formula are derived from z.
  • the following are used as comonomers: straight-chain and branched olefins having 2 to 12 carbon atoms. Examples include: ethylene, propylene, n-butylene, i-butylene, di-i-butylene and dodecene. Isobutene is preferred.
  • polymers which may be mentioned in detail are: an alternating copolymer of maleic acid and i-butene.
  • the molar masses of the polymers are generally 500 g / mol to 20,000 g / mol, preferably 700 to 2,000 g / mol.
  • the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, e.g. Maleic anhydride, since the anhydrides usually copolymerize better with the olefins.
  • the anhydride groups of the copolymers can then be reacted directly with the amines.
  • the reaction of the polymers or copolymers with the secondary fatty amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours.
  • the secondary fatty amine is in amounts of about one mole per mole of polymerized dicarboxylic acid anhydride, i.e. about 0.9 to 1.1 mol / mol applied.
  • the use of larger or smaller amounts is possible, but has no advantage. If larger amounts than one mole are used, ammonium salts are obtained in part, since the formation of a second amide group requires higher temperatures, longer residence times and water separation. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.
  • the polymers are prepared by known discontinuous or continuous polymerization processes such as bulk, suspension, precipitation or solution polymerization and initiation with customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, 2,2-butobutylobutyl, tert.
  • customary radical donors such as acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, 2,2-butobutylobutyl, tert.
  • the polymerization is generally carried out at from 40 to 400 ° C., preferably from 80 to 300 ° C., and when olefins or solvents are used, boiling temperatures below the polymerization temperature are advantageously carried out under pressure.
  • the polymerization is expediently carried out in the absence of air, i.e. if it is not possible to work under boiling conditions, e.g. B. carried out under nitrogen, since oxygen delays the polymerization.
  • the reaction can be accelerated by the use of redox coinitiators such as benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, manganese, iron, nickel and chromium.
  • the amounts usually used are 0.1 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight.
  • regulators are, for example, allyl alcohols, such as buten-1-ol-3, organic mercapto compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert.- Dodecyl mercaptan, which are generally used in amounts of 0.1% by weight to 10% by weight.
  • Suitable apparatus for the polymerization are e.g. Conventional stirred kettles with, for example, anchor, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tube reactors and static mixers.
  • the simplest method of polymerization is bulk polymerization.
  • the olefins and the acid group- or acid anhydride group-containing monomer are polymerized in the presence of an initiator and in the absence of solvents. This process is particularly suitable for those copolymers in which the olefin used has 6 or more carbon atoms.
  • all monomers are mixed in the desired composition and a small part, e.g. about 5 to 10%, in the reactor before, heated to the desired polymerization temperature with stirring and metered in the remaining monomer mixture and the initiator and optionally coinitiator and regulator evenly within 1 to 10 hours, preferably 2 to 5 hours.
  • copolymer can then be converted to the paraffin dispersant according to the invention directly in the melt or after dilution with a suitable solvent.
  • a continuous high-pressure process which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour is also suitable for producing the desired copolymers.
  • the polymerization apparatus e.g. a pressure vessel, a pressure vessel cascade, a pressure tube or a pressure vessel with a downstream reaction tube, which is provided with a static mixer, can be used.
  • the monomers are preferably polymerized from olefins and monoethylenically unsaturated compounds containing acid anhydride groups or acid groups in at least 2 polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a heatable static mixer. You get sales of more than 99%.
  • a copolymer of styrene and maleic anhydride can be prepared, for example, by continuously feeding the monomers and a suitable initiator to a reactor or two reaction zones connected in series, for example a reactor cascade, and the reaction product after a residence time of 2 to 60, preferably 5 to 30 minutes , continuously discharged from the reaction zone at temperatures between 200 and 400 ° C.
  • the polymerization is expediently carried out at pressures of more than 1 bar, preferably between 1 and 200 bar.
  • the copolymers obtained with solids contents above 99 ° C. can then be further converted to the corresponding amides.
  • solvents are used in which the monomers are soluble and the copolymer formed is insoluble and fails.
  • solvents are ethers such as diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether, toluene, xylene, ethylbenzene, cumene, high-boiling aromatic mixtures such as Solvesso 100 @, 150 and 200, aliphatic and cycloaliphatic hydrocarbons and mixtures with one another.
  • a protective colloid When carrying out the precipitation polymerization, it is expedient to use a protective colloid to prevent the formation of aggregates, in particular when working at concentrations of more than 40% by weight.
  • Suitable protective colloids are polymeric substances which are readily soluble in the solvents and which do not react with the monomers.
  • Suitable examples are copolymers of maleic anhydride with vinyl alkyl ethers and / or olefins having 8 to 20 C-atoms as well as their Monoester with C 1O - to C 20 alcohols, or mono- and diamides of C 1O - to C 20 -Alkylami NEN and polyalkyl vinyl ethers, the alkyl group of which contains 1 to 20 carbon atoms, such as polymethyl, polyethylene, polyisobutyl and polyoctadecyl vinyl ether.
  • the amounts of protective colloid added are usually 0.05 to 4% by weight (based on the monomers used), preferably 0.1 to 2% by weight, it often being advantageous to combine several protective colloids.
  • the solvent, the protective colloid and part of the monomer mixture in the reactor and to meter in the rest of the monomer mixture and the initiator and, if appropriate, the point and regulator, at the selected polymerization temperature with vigorous stirring.
  • the feed times for monomer and initiator are generally between 1 and 10 hours, preferably 2 and 5 hours. It is also possible to polymerize all of the starting materials together in one reactor, but problems with heat dissipation can occur, so that such a procedure is less appropriate.
  • the concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 to 70% by weight.
  • the polymers can be isolated directly from the polymer suspensions in evaporators, for example belt dryers, paddle dryers, spray dryers and fluidized bed dryers.
  • Another embodiment for the preparation of the copolymers is solution polymerization. It is carried out in solvents in which the monomers and the copolymers formed are soluble. All solvents that meet this requirement and that do not react with the monomers are suitable for this. For example, these are acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and dioxane.
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and part of the monomer mixture for example about 5 to 20%
  • solvent and olefins can also be introduced into the polymerization reactor and then, after the polymerization temperature has been reached, the monomers containing acid groups or acid anhydride groups, if appropriate dissolved in the solvent, and the initiator and, if appropriate, coinitiator and regulator, are metered in .
  • the concentrations of the monomers to be polymerized are between 20 and 80% by weight, preferably 30 and 70% by weight.
  • the solid copolymer can be isolated easily by evaporating the solvent. But here, too, it is expedient to choose a solvent in which the further reaction with amines can take place.
  • the additives according to the invention are added to the petroleum middle distillates in amounts of 50 to 1000 ppm, preferably 100 to 500 ppm.
  • middle distillates already contain flow improvers such as ethylene-vinyl ester copolymers.
  • Preferred copolymers (b) are those which essentially contain ethylene and 25 to 45% by weight of vinyl acetate, vinyl propionate or ethylhexyl acrylate. Also to be mentioned are copolymers which contain, for example, fumaric acid esters.
  • the molecular weight of the flow improvers is generally 500 to 5000, preferably 1000 to 3000.
  • hydrocarbon-soluble carboxylic acids and / or sulfonic acids or their salts are suitable as conductivity improvers (c) for middle distillates.
  • middle distillates The basic conductivity of middle distillates is approx. 5 to 10 ps / m, measured according to DIN 51412. Variations occur due to different contents of water, salts, naphthenic acids, phenols and others compounds containing sulfur and nitrogen.
  • metal salts of hydrocarbon-soluble carboxylic and sulfonic acids as are commercially available under the name ASA3® / Shell, and other conventional conductivity improvers, such as the commercially available Stadis @ 450 commercial product from DuPont, whose composition is not known, are also suitable.
  • Examples 1 to 5 describe the preparation of the polymers, which are then reacted with ditallow fatty amine according to Examples 6 to 11 to give the paraffin dispersants according to the invention.
  • the molecular weights were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
  • a reaction mixture of 60 g styrene / maleic anhydride copolymer and 60.2 g stearylamine in 368 g neutral oil 1A is heated to 220 ° C. for 20 hours. The mixture was then allowed to cool to 125 ° C. and 10.9 g of calcium hydroxide (dissolved in water) were metered in. After 2 hours of stirring at this temperature, the reaction mixture was filtered and the water was separated off.
  • Example 4 production according to DE 2531234, Example 2
  • the middle distillate was tested with different amounts of flow improvers alone and / or together with paraffin dispersants in combination with / without conductivity improvers at temperatures below the cloud point.
  • the cooling was carried out using a temperature program.
  • the middle distillates I (Tables I, II) were cooled from room temperature to -12 ° C at a cooling rate of 1 ° C / h and stored at -12 ° C for 24 h.
  • the experiments were carried out with 100 ml and 1000 ml middle distillate volumes.
  • Tables I - II list: volume of the sedimented paraffin phase (%) optically assessed, cloud point (CP) and cold filter plugging point (CFPP) of the lower area (lower 40% by volume), CP and CFPP of the upper area (upper 60 vol.%) As well as the CP and CFPP of the middle distillate containing the additives before the storage test.
  • the sedimentation of the paraffins is additionally reduced by adding conductivity-improving additives.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (3)

1. Distillats moyens du pétrole stables au froid, contenant, à titre d'agents d'amélioration de l'écoulement ou de la fluidité, des proportions actives de copolymères, qui se composent exclusivement d'oléfines à chaînes droites et ramifiées de 2 à 12 atomes de carbone et d'unités de la formule 1 :
Figure imgb0008
dans laquelle R3 et R4 représentent des radicaux alkyle qui comportent de 14 à 24 atomes de carbone.
2. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce qu'ils contiennent les copolymères en proportions de 50 à 1000 ppm.
3. Distillats moyens du pétrole suivant la revendication 1, caractérisés en ce qu'ils contiennent, complémen- tairement :
A) 50 à 1000 ppm d'agents d'amélioration de l'écoulement de la fluidité, choisis dans le groupe constitué de copolymères de l'éthylène et de l'acétate de vinyle, de l'éthylène et du propionate de vinyle et de l'éthylène et de l'acrylate de vinylhexyle, avec un poids moléculaire moyen de 1000 à 5000, et
B) 0,1 à 40 ppm d'agents d'amélioration de la conductibilité.
EP90123728A 1989-12-16 1990-12-10 Distillat moyen de pétrole stable au froid contenant des copolymères comme dispersants de paraffine Expired - Lifetime EP0436151B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90123728T ATE94896T1 (de) 1989-12-16 1990-12-10 Kaeltestabile erdoelmitteldestillate, enthaltend polymere als paraffindispergatoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3941561 1989-12-16
DE3941561A DE3941561A1 (de) 1989-12-16 1989-12-16 Kaeltestabile erdoelmitteldestillate, enthaltend polymere als paraffindispergatoren

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EP0436151A1 EP0436151A1 (fr) 1991-07-10
EP0436151B1 true EP0436151B1 (fr) 1993-09-22
EP0436151B2 EP0436151B2 (fr) 1997-08-27

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AT (1) ATE94896T1 (fr)
CA (1) CA2032246A1 (fr)
DE (2) DE3941561A1 (fr)
ES (1) ES2059967T5 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0857776A1 (fr) 1997-01-07 1998-08-12 Clariant GmbH Amélioration de la fluidité d'huiles minérales et de distillates d'huiles minérales par l'utilisation de résines alkylphénol-aldéhyde
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2110124T3 (es) * 1993-01-06 1998-02-01 Clariant Gmbh Termopolimeros a base de anhidridos de acidos carboxilicos alfa,beta-insaturados, de compuestos alfa,beta-insaturados y de polioxialquileneteres de alcoholes inferiores insaturados.
DE69415095T2 (de) * 1993-07-27 1999-05-20 Shell Internationale Research Maatschappij B.V., Den Haag/S'gravenhage Polymere fliessverbesserte Zusätze
JP2001505971A (ja) * 1996-11-22 2001-05-08 クラリアント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 水和ガスの形成を抑制するための添加剤
DE19816797C2 (de) * 1998-04-16 2001-08-02 Clariant Gmbh Verwendung von stickstoffhaltigen Ethylencopolymeren zur Herstellung von Brennstoffölen mit verbesserter Schmierwirkung
DE102004014080A1 (de) * 2004-03-23 2005-10-13 Peter Dr. Wilharm Nukleierungsmittel auf der Basis von hyperverzweigten Polymeren
EP2025737A1 (fr) 2007-08-01 2009-02-18 Afton Chemical Corporation Compositions de combustibles sans danger pour l'environnement
GB201111799D0 (en) 2011-07-08 2011-08-24 Innospec Ltd Improvements in fuels
GB201201550D0 (en) * 2012-01-30 2012-03-14 Innospec Ltd Improvements in or relating to fuels
EP3885424A1 (fr) 2020-03-24 2021-09-29 Clariant International Ltd Compositions et procédés de dispersion des paraffines dans des huiles de combustible à faible teneur en soufre
EP4074810B1 (fr) 2021-04-15 2023-11-15 Basf Se Nouvelles compositions de réduction de la cristallisation de cristaux de paraffine dans des carburants
WO2024037904A1 (fr) * 2022-08-16 2024-02-22 Basf Se Composition pour réduire la cristallisation de cristaux de paraffine dans des combustibles
WO2025021688A1 (fr) 2023-07-26 2025-01-30 Shell Internationale Research Maatschappij B.V. Compositions de carburant à base d'essence
WO2025093375A1 (fr) 2023-11-03 2025-05-08 Shell Internationale Research Maatschappij B.V. Compositions de carburant

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1147212A (fr) * 1955-03-22 1957-11-20 California Research Corp Composition combustible à base d'hydrocarbure
FR1527669A (fr) * 1963-08-12 1968-06-07 Socony Mobil Oil Co Compositions hydrocarbonées liquides perfectionnées
US3578421A (en) * 1968-07-26 1971-05-11 Mobil Oil Corp Liquid hydrocarbon compositions containing reaction products of an amine and methyl vinyl ether-maleic anhydride copolymers as anti-static agents
FR2030358A1 (fr) * 1969-02-07 1970-11-13 Mobil Oil Corp
GB1300227A (en) * 1969-05-09 1972-12-20 Exxon Research Engineering Co Flow improvers
US4121026A (en) * 1973-03-23 1978-10-17 Petrolite Corporation Copolymers of alpha-olefins and maleic anhydride reacted with amines in the presence of Lewis acids
NL8002689A (nl) * 1980-05-09 1981-12-01 M & T Chemicals Bv Polymeren met biocide eigenschappen.
GB8706369D0 (en) * 1987-03-18 1987-04-23 Exxon Chemical Patents Inc Crude oil

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0857776A1 (fr) 1997-01-07 1998-08-12 Clariant GmbH Amélioration de la fluidité d'huiles minérales et de distillates d'huiles minérales par l'utilisation de résines alkylphénol-aldéhyde
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole

Also Published As

Publication number Publication date
DE59002844D1 (de) 1993-10-28
EP0436151A1 (fr) 1991-07-10
ES2059967T3 (es) 1994-11-16
ES2059967T5 (es) 1997-10-16
ATE94896T1 (de) 1993-10-15
EP0436151B2 (fr) 1997-08-27
CA2032246A1 (fr) 1991-06-17
DE3941561A1 (de) 1991-06-20

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