EP0436151A1 - Distillat moyen de pétrole stable au froid contenant des polymères comme dispersants de paraffine - Google Patents
Distillat moyen de pétrole stable au froid contenant des polymères comme dispersants de paraffine Download PDFInfo
- Publication number
- EP0436151A1 EP0436151A1 EP90123728A EP90123728A EP0436151A1 EP 0436151 A1 EP0436151 A1 EP 0436151A1 EP 90123728 A EP90123728 A EP 90123728A EP 90123728 A EP90123728 A EP 90123728A EP 0436151 A1 EP0436151 A1 EP 0436151A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymers
- middle distillates
- petroleum middle
- polymers
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- QUISWUAUMRRNFA-UHFFFAOYSA-N n-docosyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCCCCCC QUISWUAUMRRNFA-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000000214 vapour pressure osmometry Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—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, 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
- C10L1/188—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, 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
-
- 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
- C10L1/197—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
-
- 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
- C10L1/24—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 "card house structure" 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.
- Well-effective 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, which filters in motor vehicles and heating systems pass 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 a little above the Bottom of the container takes place, there is a risk that the high concentration of solid paraffins leads 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, are used.
- reaction products of monoamines with maleic anhydride polymers to the corresponding imides are also described, with the use of less than one mole of amine per mole of maleic anhydride unit to neutralize remaining carboxyl groups.
- 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.
- R1 and R2 independently of one another are hydrogen or low molecular weight alkyl or together represent a tetramethylene radical and in which
- R3 and R4 are unbranched alkyl radicals with 14 to 24 carbon atoms, meet this requirement.
- Particularly suitable polymers are those which contain recurring units of the formula I, preferably those with units of the formula I '
- Copolymers of styrene with maleic anhydride are particularly preferred.
- radicals of the formula I are derived from z. B. maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and of the copolymers. Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins with 2 to 12 carbon atoms, and mixtures with one another.
- Examples include: styrene, ⁇ -methylstyrene, dimethylstyrene, ⁇ -ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, i-butylene, di-i-butylene and dodecene. Styrene and isobutene are preferred, styrene is particularly preferred.
- polymers which may be mentioned in detail are: polymaleic acid, a molar, alternating styrene / maleic acid copolymer, randomly constructed styrene / maleic acid copolymers in a ratio of 10:90 to 90:10 and an alternating copolymer of maleic acid and i-butene.
- the molar masses of the polymers are generally from 500 g / mol to 20,000 g / mol, preferably from 700 to 2000 g / mol.
- Dialkylamines of the formula come as amines: considered in the
- R3, R4 is a straight-chain alkyl radical having 14 to 24 carbon atoms.
- Dioleylamine, dipalmitinamine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.
- the dicarboxylic acids in the form of the anhydrides, e.g. Maleic anhydride, citraconic anhydride and tetrahydrophthalic 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 used in amounts of approximately one mole per mole of polymerized dicarboxylic acid anhydride, ie approximately 0.9 to 1.1 moles / mole.
- 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 the elimination of water. If amounts smaller 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 peroxidicylate, 2,2'-azodobio-butylate, tert.-butodoboxylate, tert.-butodobio-butylate, tert-butyl-tert-butyl-tert-butyl-tert-butyl-tert (4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, tert-butyl per-2-ethyl hexanoate, tert-butyl permaleinate, 2,2'-azobis (isobutyronitrile), bis (tert-buty
- 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 advantageously carried out in the absence of air, ie 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.
- Equipment suitable for the polymerization is e.g. Conventional stirred kettles with, for example, armature, blade, impeller or multi-stage impulse countercurrent stirrers and for the continuous production of stirred kettle cascades, tubular 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 and 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 is also suitable for producing the desired copolymers, which permits space-time yields of 1 to 50 kg of polymer per liter of reactor and hour.
- a polymerization 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 as the polymerization apparatus.
- 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, at temperatures between 200 and 400 ° C continuously discharged from the reaction zone.
- 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.
- copolymers of maleic anhydride with vinyl alkyl ethers and / or olefins with 8 to 20 C atoms and their monoesters with C10 to C20 alcohols or mono- and diamides with C10 to C20 alkyl amines and polyalkyl vinyl ethers whose alkyl group is 1 to 20 C are suitable Contains atoms, such as polymethyl, polyethyl, 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 polymer suspensions can be used directly in evaporators, for example belt dryers polymers, 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.
- 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 other compounds containing sulfur and nitrogen.
- metal salts of hydrocarbon-soluble carboxylic and sulfonic acids as are commercially available under the name ASA3®Shell, as well as 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 32.1 g of the polymer suspension according to Example 3 and 77.2 g of ditallow fatty amine was first stirred at 80 ° C. for 1.5 hours and then again at 150 ° C. for 7 hours. 94.6 g of the product were obtained as a yellow-brown, viscous oil.
- a reaction mixture of 60 g styrene / maleic anhydride copolymer and 60.2 g stearylamine in 368 g neutral oil IA 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 13 (Production according to DE 2531234, Example 2)
- middle distillate I, II, III where I and II mean diesel fuel and III heating oil EL.
- the middle distillates were 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, II (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 middle distillate III (Table III) was also cooled from approx. 20 ° C 1 ° C / h to -4 ° C and stored at -4 ° C / 24 h.
- the experiments were carried out with 100 ml and 1000 ml middle distillate volumes.
- Tables I - III list: volume of the sedimented paraffin phase (%) optically assessed, cloud point (CP) and cold filter plugging point (CFPP) of the lower area (lower 40 vol%), 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.
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0436151A1 true EP0436151A1 (fr) | 1991-07-10 |
EP0436151B1 EP0436151B1 (fr) | 1993-09-22 |
EP0436151B2 EP0436151B2 (fr) | 1997-08-27 |
Family
ID=6395577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90123728A Expired - Lifetime EP0436151B2 (fr) | 1989-12-16 | 1990-12-10 | Distillat moyen de pétrole stable au froid contenant des copolymères comme dispersants de paraffine |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0436151B2 (fr) |
AT (1) | ATE94896T1 (fr) |
CA (1) | CA2032246A1 (fr) |
DE (2) | DE3941561A1 (fr) |
ES (1) | ES2059967T5 (fr) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998023843A1 (fr) * | 1996-11-22 | 1998-06-04 | Clariant Gmbh | Additifs pour empecher la formation d'hydrates de gaz |
US5998530A (en) * | 1997-01-07 | 1999-12-07 | Clariant Gmbh | Flowability of mineral oils and mineral oil distillates using alkylphenol-aldehyde resins |
EP0964052A1 (fr) * | 1998-04-16 | 1999-12-15 | Clariant GmbH | Utilisation de copolymères d'éthylène contenant de l'azote pour la production d'huiles combustibles à action lubrifiante améliorée |
DE102004014080A1 (de) * | 2004-03-23 | 2005-10-13 | Peter Dr. Wilharm | Nukleierungsmittel auf der Basis von hyperverzweigten Polymeren |
WO2013007994A1 (fr) | 2011-07-08 | 2013-01-17 | Innospec Limited | Amélioration apportée aux propriétés d'écoulement à froid de combustibles |
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 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK0606055T3 (da) * | 1993-01-06 | 1998-04-14 | Clariant Gmbh | Terpolymerer på basis af alfa,beta-umættede dicarboxylsyreanhydrider, alfa-beta-umættede forbindelser og polyoxyalkylenethere af lavere umættede alkoholer |
BR9402930A (pt) * | 1993-07-27 | 1995-04-11 | Shell Int Research | Copolímero de pelo menos um (met)acrilato de N-(alquila C8-C30) com anidrido maléico, que contém unidades monoméricas alternadas de (met)acrilato e anidrido maléico, processo para a preparação de um copolímero, composição de óleo hidrocarbonete e, use de respectivo copolímero |
EP2025737A1 (fr) | 2007-08-01 | 2009-02-18 | Afton Chemical Corporation | Compositions de combustibles sans danger pour l'environnement |
GB201201550D0 (en) * | 2012-01-30 | 2012-03-14 | Innospec Ltd | Improvements in or relating to fuels |
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 |
Citations (8)
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 |
DE2022588A1 (de) * | 1969-05-09 | 1970-11-12 | Esso Res And Engineering Co | Fliessverbesserer |
FR2030358A1 (fr) * | 1969-02-07 | 1970-11-13 | Mobil Oil Corp | |
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 |
US4163645A (en) * | 1973-03-23 | 1979-08-07 | Petrolite Corporation | Organic liquids containing anti-static agents which are copolymers of alpha-olefins and maleic anhydrides reacted with amines |
EP0040498A1 (fr) * | 1980-05-09 | 1981-11-25 | M & T Chemicals B.V. | Polymères à propriétés biocides |
EP0283293A1 (fr) * | 1987-03-18 | 1988-09-21 | Exxon Chemical Patents Inc. | Utilisation d'agents améliorant l'écoulement à basse température dans des huiles combustibles distillées |
-
1989
- 1989-12-16 DE DE3941561A patent/DE3941561A1/de not_active Withdrawn
-
1990
- 1990-12-10 AT AT90123728T patent/ATE94896T1/de not_active IP Right Cessation
- 1990-12-10 ES ES90123728T patent/ES2059967T5/es not_active Expired - Lifetime
- 1990-12-10 EP EP90123728A patent/EP0436151B2/fr not_active Expired - Lifetime
- 1990-12-10 DE DE90123728T patent/DE59002844D1/de not_active Expired - Lifetime
- 1990-12-14 CA CA002032246A patent/CA2032246A1/fr not_active Abandoned
Patent Citations (8)
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 | |
DE2022588A1 (de) * | 1969-05-09 | 1970-11-12 | Esso Res And Engineering Co | Fliessverbesserer |
US4163645A (en) * | 1973-03-23 | 1979-08-07 | Petrolite Corporation | Organic liquids containing anti-static agents which are copolymers of alpha-olefins and maleic anhydrides reacted with amines |
EP0040498A1 (fr) * | 1980-05-09 | 1981-11-25 | M & T Chemicals B.V. | Polymères à propriétés biocides |
EP0283293A1 (fr) * | 1987-03-18 | 1988-09-21 | Exxon Chemical Patents Inc. | Utilisation d'agents améliorant l'écoulement à basse température dans des huiles combustibles distillées |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998023843A1 (fr) * | 1996-11-22 | 1998-06-04 | Clariant Gmbh | Additifs pour empecher la formation d'hydrates de gaz |
US6544932B2 (en) | 1996-11-22 | 2003-04-08 | Clariant Gmbh | Additives for inhibiting gas hydrate formation |
US5998530A (en) * | 1997-01-07 | 1999-12-07 | Clariant Gmbh | Flowability of mineral oils and mineral oil distillates using alkylphenol-aldehyde resins |
EP0964052A1 (fr) * | 1998-04-16 | 1999-12-15 | Clariant GmbH | Utilisation de copolymères d'éthylène contenant de l'azote pour la production d'huiles combustibles à action lubrifiante améliorée |
DE102004014080A1 (de) * | 2004-03-23 | 2005-10-13 | Peter Dr. Wilharm | Nukleierungsmittel auf der Basis von hyperverzweigten Polymeren |
WO2013007994A1 (fr) | 2011-07-08 | 2013-01-17 | Innospec Limited | Amélioration apportée aux propriétés d'écoulement à froid de combustibles |
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 |
WO2021190794A1 (fr) | 2020-03-24 | 2021-09-30 | Clariant International Ltd | Compositions et procédés de dispersion de paraffines dans des huiles combustibles à faible teneur en soufre |
WO2021190793A1 (fr) | 2020-03-24 | 2021-09-30 | Clariant International Ltd | Compositions et procédés de dispersion de paraffines dans des huiles combustibles à faible teneur en soufre |
US11993756B2 (en) | 2020-03-24 | 2024-05-28 | Clariant International Ltd | Compositions and methods of dispergating paraffins in sulphur-low fuel oils |
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 |
Also Published As
Publication number | Publication date |
---|---|
EP0436151B2 (fr) | 1997-08-27 |
ES2059967T3 (es) | 1994-11-16 |
EP0436151B1 (fr) | 1993-09-22 |
DE59002844D1 (de) | 1993-10-28 |
ES2059967T5 (es) | 1997-10-16 |
DE3941561A1 (de) | 1991-06-20 |
CA2032246A1 (fr) | 1991-06-17 |
ATE94896T1 (de) | 1993-10-15 |
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