EP1294832B1 - Additives for improving the cold flow properties and the storage stability of crude oil - Google Patents
Additives for improving the cold flow properties and the storage stability of crude oil Download PDFInfo
- Publication number
- EP1294832B1 EP1294832B1 EP01957827A EP01957827A EP1294832B1 EP 1294832 B1 EP1294832 B1 EP 1294832B1 EP 01957827 A EP01957827 A EP 01957827A EP 01957827 A EP01957827 A EP 01957827A EP 1294832 B1 EP1294832 B1 EP 1294832B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- additive
- mol
- carbon atoms
- radicals
- 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.)
- Expired - Lifetime
Links
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
- C10L1/143—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
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1981—Condensation polymers of aldehydes or ketones
-
- 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 present invention relates to an additive composition Flow improvers, poly- ⁇ -olefins and organic acids, and their Use to improve the cold flow and storage properties of Crude oils.
- Crude oils, residual oils, oil distillates e.g. Diesel fuel, mineral oils, Lubricating oils, hydraulic oils, etc. contain depending on their origin or the nature of their Processing more or less large amounts of n-paraffins and asphaltenes, which pose particular problems because they decrease in temperature crystallize out or agglomerate and thereby deteriorate the Flow properties of these oils can lead. This deterioration in The flow properties of the oils are known as "stagnation" of the oil.
- the Pour point is the standardized name for the temperature at which an oil, e.g. Mineral oil, diesel fuel or hydraulic fluid when cooling down just stops flowing. However, the pour point is not identical to the so-called pour point.
- the pour point is non-specific, not by Standard-covered term for the temperature at which a solid begins to flow under given measuring conditions. Through the The flow properties can then deteriorate, for example, when Transportation, storage and / or processing of these oils containers, Pipes, valves or pumps are blocked, especially if they contain paraffin Oils that are difficult to inhibit. Also require Paraffin precipitation increased pressures when restarting pipelines (Yield Point).
- US-3,567,597 describes mineral oil distillates containing crude oils, shale oils and residual oils which, as pour point depressants, contain a copolymer of ethylene and a vinyl ester of a saturated aliphatic C 1 to C 30 monocarboxylic acid, the copolymer having an average molecular weight of 4,000 to 60,000 and Contains 40 to 95 wt .-% ethylene.
- DE-A-20 57 168 discloses a method for reducing the flow of friction in oily liquids flowing through lines and a small amount Concentrations of effective, shear-resistant additive with which the Reduce friction losses in oily liquids. This is the Liquids a small amount of at least one high molecular weight polymer added, which is derived from at least one ⁇ -olefin having 6 to 20 carbon atoms (Polyolefin).
- EP-A-0 176 641 discloses that the properties of poly- ⁇ -olefins are known as This will improve flow accelerators for liquid hydrocarbons leave that the polymerization of the ⁇ -olefins by the Ziegler method in Presence of a dialkyl aluminum halide and one Trialkylaluminum compound performs.
- GB-A-2 305 437 discloses pour point depressants for crude oils. These include a reaction product from an alkylphenol with an average of more than 30 carbon atoms in the alkyl radical, with an aldehyde with 1 to 12 carbon atoms. This pour point Depressants are suitable for treating crude oils that have a pour point above 4 ° C.
- EP-A-0 311 452 discloses additives for improving the cold flow behavior of Fuel and lubricating oils. These additives include an alkylphenol aldehyde resin with a molecular weight of at least 3000, which has 6 to 50 carbon atoms in the alkyl radical and has a specified distribution of the carbon chain lengths the alkyl residue shows.
- US 3,735,770 discloses a method for improving the flowability of Crude oils in the cold. This process involves the addition of copolymers Ethylene with unsaturated carboxylic acid esters, or from alkylphenols to oil.
- EP-A-0 857 776 discloses mixtures of ethylene copolymers, alkylphenol-formaldehyde resins and optionally paraffin dispersants (polar nitrogenous compounds) to improve the cold properties of Mineral oils. These blends show up in paraffin-rich crude oils with long chain However, paraffins are not sufficiently effective.
- a disadvantage of the known flow improvers for crude and residue oils in many cases still insufficient effectiveness and the resulting resulting high use concentrations, especially with oils with high Proportion of long-chain n-paraffins with more than 30 carbon atoms.
- the known flow improvers also favor by lowering the Viscosity of the additive oil the sedimentation of the failed, specific heavier wax crystals.
- High-molecular poly- ⁇ -olefins can do that To improve the flow behavior of oils, but they do not improve them Low-temperature behavior.
- Additives are therefore sought which have improved properties as Pour point lower, i.e. which even with low doses have sufficient effectiveness and in comparison with pour point depressants of the prior art with a lower concentration Have their own pour point and with a variety of oils, especially at paraffinic oils are effective.
- the additive is supposed to lower the cloud point, reduce the viscosity and yield point of the oil in the cold, and the Delay or prevent sedimentation of the failed paraffin crystals.
- Another object of the invention are mineral oils that described Contain mixtures of the components A), B), and C).
- Another object of the invention is the use of these Composition to improve cold flow properties and Storage stability of mineral oils.
- the mixtures according to the invention preferably contain 2 to 30% by weight, especially 5 to 25% by weight of copolymer A), 25 to 70% by weight, especially 30 to 60 % By weight poly- ⁇ -olefin B) and 5 to 65% by weight, especially 10 to 50% by weight organic acid C).
- Suitable vinyl esters include vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, neononane, neodecanoic and neoundecanoic acid vinyl esters. Vinyl acetate and vinyl propionate are particularly preferred.
- Suitable acrylic esters include methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n-, iso- and tert-butyl acrylate and 2-ethylhexyl acrylate, as well as the corresponding esters of methacrylic acid.
- the copolymers of constituent A1) can also comprise up to 5 mol% of structural units of alkyl vinyl ethers and / or olefins.
- the olefins are preferably alkenes with 3 to 30, especially with 3 to 10 carbon atoms.
- Suitable olefins are for example propene, butene, isobutene, pentene, hexene, isohexene, diisobutylene and norbornene.
- alkyl radicals R 4 , R 6 and R 7 can carry minor amounts of functional groups such as amino, amido, nitro, cyano, hydroxyl, keto, carbonyl, carboxy, ester, sulfo groups or halogen atoms, as long as these do not significantly impair the hydrocarbon character of the radicals mentioned.
- the molecular weight of the copolymers of component A1) is preferably between 1000 and 100,000 units, which according to DIN 53735 at 190 ° C and a tracking force of 2.16 kg measured MFI values between 0.1 and Corresponds to 1000g / 10 min.
- ethylene / vinyl acetate ethylene / vinyl propionate, Ethylene / versatic acid vinyl ester, ethylene / vinyl acetate / versatic acid vinyl ester, Ethylene / vinyl acetate / diisobutylene, ethylene / vinyl acetate / 4-methylpentene and To name ethylene / vinyl acetate / isobutylene copolymers.
- the copolymers A1) are prepared by known processes (see here e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A 21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably turns the high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the comonomers is initiated by radical initiators (radical chain initiators). To this class of substances belongs e.g.
- Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
- the Initiators are used individually or as a mixture of two or more substances Amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the comonomer mixture used.
- the desired melt viscosity of the copolymers A1) is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
- Hydrogen, saturated or unsaturated hydrocarbons e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
- the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
- High pressure bulk polymerization is carried out in known high pressure reactors, e.g.
- Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful.
- Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free working method has proven particularly successful.
- the embodiment of the polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the Reactor entrance and fed via one or more side branches. in this connection the comonomer streams can be composed differently (EP-B-0 271 738).
- Preferred copolymers A2) contain 80-100 mol% of the recurring structural element of the formula 5 where R 8 and R 9 independently of one another are hydrogen, phenyl or a group of the formula COOR 11 , R 10 is hydrogen, methyl or a group of the formula -CH 2 COOR 11 and R 11 is a C 10 - to C 30 - Alkyl or alkylene radical, preferably a C 12 to C 26 alkyl or alkylene radical, with the proviso that these recurring structural units contain at least one and at most two carboxylic acid ester units in one structural element.
- Copolymers in which R 8 and R 9 are hydrogen or a group of the formula COOR 11 and R 10 are hydrogen or methyl are particularly suitable.
- These structural units are derived from esters of monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, cinnamic acid, or from semi- or diesters of dicarboxylic acids, such as, for example, maleic acid, fumaric acid and itaconic acid.
- esters of acrylic acid are particularly preferred.
- Suitable alcohols are those with 10-30 carbon atoms, especially those with 12-26 carbon atoms such as 1-decanol, 1-dodecanol, 1-tridecanol, Isotridecanol, 1-tetradecanol, 1-hexadecanol, eicosanol, docosanol, Tetracosanol, hexacosanol and naturally occurring mixtures such as Coconut fatty alcohol, tallow fatty alcohol and behenyl alcohol.
- the alcohols can be of natural as well as synthetic origin.
- the copolymers of component A2) can contain up to 20 mol%, preferably up to 10 mol%, of comonomers such as vinyl esters of the formula 2, (meth) acrylic esters of the formula 3, alkyl vinyl ethers of the formula 4 and / or olefins.
- heteroatoms bearing ethylenically unsaturated compounds such as allyl polyglycols, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dimethylaminoethyl acrylate, perfluoroalkyl acrylate, and the corresponding esters and amides of methacrylic acid, vinyl pyridine, vinyl pyrrolidone, acrylic acid, methacrylic acid, p-acetoxystyrene, and vinyl methoxyacetate as comonomers in Component A2) suitable.
- allyl polyglycols benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dimethylaminoethyl acrylate, perfluoroalkyl acrylate, and the corresponding esters and amides of methacrylic acid, vinyl pyridine, vinyl pyrroli
- the molecular weights or molecular weight distributions of the invention Copolymers have a K value (measured according to Fikentscher in 5% Solution in toluene) characterized from 10 to 100, preferably 15 to 80.
- the Molecular weights Mw can range from 2,000 to 500,000, preferred 5,000 to 300,000 and for example by means of gel permeation chromatography against polystyrene standards.
- the copolymers A2) are prepared by (co) polymerizing esters ethylenically unsaturated carboxylic acids, especially (meth) acrylates, optionally with other comonomers according to conventional radicals Polymerization.
- a suitable manufacturing process is to combine the monomers in one dissolve organic solvents and in the presence of a radical initiator Polymerize temperatures in the range of 30 to 150 ° C.
- a solvent are aromatic hydrocarbons such. B. toluene, xylene, Trimethylbenzene, dimethylnaphthalene or mixtures of these aromatic Hydrocarbons.
- aromatic Hydrocarbons such as Solvent Naphtha or Shellsol AB® (manufacturer: Shell) are used.
- Aliphatic solvents are also suitable Suitable for hydrocarbons.
- alkoxylated aliphatic alcohols or their Esters such as Butyl glycol is used as a solvent, but is preferred as a mixture with aromatic hydrocarbons.
- starters such as azo-bisisobutyronitrile, Esters of peroxycarboxylic acids such as e.g. t-butyl perpivalate and t-Butyl-per-2-ethylhexanoate or dibenzoyl peroxide is used.
- the polymers which form component B are poly- ⁇ -olefins which differ from Allow monoolefins with 3.4 or 5 carbon atoms to be derived.
- Especially preferred mono-olefins as the base of suitable polyolefins are propylene and isobutylene, of which polypropylene and polyisobutylene as polyolefins arise. You can also use minor amounts, preferably less than 10 mol% of longer-chain ⁇ -olefins with 6 to 50, preferably 12 to 40 Contain carbon atoms.
- Suitable olefins are 1-dodecene, 1-tetradecene, 1-tridecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-Nonadecen, 1-Eicosen, 1-Hemicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, 1-Octacoses etc. and their mixtures.
- the polyolefins B) are accessible by ionic polymerization, and as Commercial products available (e.g. ®Ultravis, ®Napvis, ®Hyvis, ®Glissopal) (Polyisobutenes from BP, BASF with different alkyl vinylidene contents and Molecular weights).
- the distribution of the olefin isomers resulting from various polymerization processes is generally of minor importance for the use according to the invention, but in special cases poly- ⁇ -olefins with an increased alkylvinylidene content of more than 50 mol%, in particular more than 70 mol% proven to be advantageous.
- Alkyl vinylidene content means the content of the polyolefins in structural units with terminal double bonds which are based on compounds of the formula 7 decrease in which R 16 or R 17 is methyl or ethyl and the other group is an oligomer of the C 3 -C 5 olefin.
- the number of carbon atoms of the poly- ⁇ -olefin is between 35 and 350. In a preferred embodiment of the invention, the number of carbon atoms is between 45 and 250.
- Component C1) is an alkylphenol-aldehyde resin. These are known in principle and for example in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351 ff.
- the alkyl radicals R 1 and R 2 of the alkylphenol can be the same or different in the alkylphenol-aldehyde resins C1) used in the additive according to the invention and have 1 to 30, preferably 4 to 20 carbon atoms; it is preferably n-, i- and tert-butyl, n- and i-pentyl, n- and i-hexyl, n- and i-octyl, n- and i-nonyl, n- and i-decyl , n- and i-dodecyl, tripropenyl, tetrapropenyl and pentapropenyl.
- the phenol is preferably monoalkylated.
- the aliphatic aldehyde in the alkylphenol-aldehyde resin C1) has 1 to 4 Carbon atoms and is preferably formaldehyde.
- the average molecular weight the alkylphenol-aldehyde resins are preferably 400-10,000, in particular 400 - 5000 g / mol.
- the prerequisite here is that the resins are oil-soluble.
- the alkylphenol-aldehyde resins C1) are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acid catalysis, where novolak-type condensation products arise.
- the condensates obtained according to both types are as additive component C1) suitable.
- the condensation in the presence of acidic catalysts is preferred.
- a mono- and / or Dialkylphenol with 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms each Alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 4 carbon atoms reacted with each other about per mole of alkylphenol compound 0.5-2 mol, preferably 0.7-1.3 mol, of aldehyde can be used.
- Suitable alkylphenols are in particular C 4 -C 20 alkylphenols such as, for example, o- or p-cresol, n-, sec.- and tert. Butylphenol, n- and i-pentylphenol, n- and i-hexylphenol, n- and i-octylphenol, n- and i-nonylphenol, n- and i-decylphenol, n- and 1-dodecylphenol, tripropenylphenol, tetrapropenylphenol and pentapropenylphenol.
- the corresponding dialkylated phenols are likewise suitable, it being possible for the alkyl radicals to be the same or different.
- aldehydes are formaldehyde, acetaldehyde and Butyraldehyde, formaldehyde is preferred.
- the formaldehyde can take the form of Paraformaldehyde or in the form of a preferably 20 to 40 wt .-% aqueous formalin solution can be used. It can also be corresponding Amounts of trioxane can be used.
- alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic Acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acids, Sulfamido acids or haloacetic acids, and in the presence of one with water an azeotropic organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof.
- the reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, which water of reaction formed during the reaction by azeotropic Distillation is removed.
- Solvents that are under the conditions of Condensation no protons can split off after the condensation reaction stay in the products.
- the resins can be used directly or after neutralization of the Catalyst are used, optionally after further dilution of the Solution with aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Solvesso 250, ®Exxsol, ®ISOPAR and Shellsol D types.
- aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, eth
- Constituent C2 is organic, oil-soluble sulfonic acids or their metal or ammonium salts, preferably alkali metal salts.
- Aliphatic sulfonic acids such as alkane sulfonates having 8 to 30, particularly preferably 10 to 26, in particular 12 to 24, carbon atoms are preferred.
- the sulfone group can be terminal or attached to a methylene group on the hydrocarbon chain.
- Aromatic sulfonic acids with one or two C 8 to C 30 , in particular C 12 to C 24 alkyl or alkenyl radicals and 1 or 2 aromatic rings are further preferred.
- the alkyl or alkenyl radicals can be linear or branched and can be attached at any point on the aromatic system.
- They are preferably in the para position to the sulfone group in systems monosubstituted with alkyl or alkenyl radicals and in the ortho and para position to the sulfone group in systems disubstituted with alkyl or alkenyl radicals.
- Examples include: nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, nonylnaphthalenesulfonic acid, dinonylbenzenesulfonic acid and didodecylbenzenesulfonic acid.
- Oil-soluble in the sense of the invention means that at least 10% by weight is preferred at least 1% by weight, in particular at least 0.1% by weight of the additive in addition additive middle distillate becomes clearly soluble. This definition is analogous apply if the term oil-soluble is used elsewhere.
- the additives according to the invention are particularly suitable, the flowability and paraffin sedimentation of crude oils and other paraffinic mineral oils to improve, whose paraffin sediments larger portions (preferably more than 20 area% according to GC, in particular 30 to 60 area%, especially 40 to 50 Area%) of n-paraffins with carbon chain lengths of 30 and more carbon atoms exhibit. These oils are usually dark due to asphaltenes and resins colored, but they are preferably transparent. Furthermore, the Additives according to the invention are able to determine the yield point of the additive oils lower and thus facilitate the restarting of pipelines.
- the additive components according to the invention can be separated from the mineral oils or added in a mixture.
- Suitable solvents or dispersing agents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g.
- the additives according to the invention or the oils additized with them can contain other cold additives such as polar nitrogenous ones Compounds or polyoxyalkylene ethers. Furthermore, they can Corrosion inhibitors, detergent additives, defoamers, demulsifiers, Contain asphalt dispersants and other additives.
- the addition of this Additives to the oil can be used together with the invention Additive components or separately.
- additive compositions Example No. Weight fraction of the ingredients A B C D 1 1 (A1) 2 (B1) 2 (C1) - 2 1 (A1) 2 (B1) 1 (C1) 1 3 2 (A1) 1 (B1) 2 (C1) - 4 1 (A1) 1 (B1) 1 (C1) - 5 2 (A1) 1 (B1) 1 (C1) - 6 1 (A2) 2 (B1) 2 (C1) - 7 1 (A3) 2 (B1) 2 (C1) - 8th 1 (A1) 2 (B2) 2 (C1) - 9 1 (A1) 2 (B3) 2 (C1) - 10 1 (A1) 2 (B4) 2 (C1) - 11 1 (A1) 43 (B5) 10 (C2) - 12 1 (A1) 43 (B5) 10 (C3) -
- the yield point is a measure of the force that has to be exerted in order to bring the stocked crude oil back into the flowing state ("restartability").
- a force of approx. 2.2 Pa must be applied at -20 ° C, while only 0.6 - 0.7 Pa is required for the treated crude oil (500 ppm, example 1) at the same temperature.
- Example 6 Yield point in Pa for untreated crude oil and for crude oil with 500 ppm additive according to Example 1, 3, 5 or 6 temperature Crude oil untreated example 1
- Example 3 Example 5
- Example 6 - 20th 2.2 0.7 0.95 0.9 0.6 - 15th 1.55 0.6 0.8 0.7 0.5 - 10th 1 0.25 0.3 0.3 0.2 - 5th 0.75 0.1 0.1 0.1 0.1 0 0.4 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
- constituents A, B and C of the composition according to the invention were used alone or in combinations of two to improve the cold flow properties of crude oil.
- the following table shows the yield point (YP), viscosity (V) and dispersion (D) as previously described for the compositions given.
- the amount of additive was always 500 ppm. Comparative tests E.g.
- V1 500 (A1) - - 0.9 45 5 V2 - 500 (B1) - 0.95 43 5 V3 - - 500 0.92 45 7 V4 500 (A2) - - 0.88 42 9 V5 250 (A2) - 250 0.7 41 12 V6 250 (A2) 250 (B1) - 0.75 41 11 V7 - 250 (B1) 250 0.76 42 12
Landscapes
- 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)
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft eine Additivzusammensetzung aus Fließverbesserem, Poly-α-olefinen und organischen Säuren, sowie deren Verwendung zur Verbesserung der Kaltfließ- und Lagereigenschaften von Rohölen.The present invention relates to an additive composition Flow improvers, poly-α-olefins and organic acids, and their Use to improve the cold flow and storage properties of Crude oils.
Rohöle, Rückstandsöle, Öldestillate, wie z.B. Dieselkraftstoff, Mineralöle, Schmieröle, Hydrauliköle usw. enthalten je nach ihrer Herkunft oder der Art ihrer Verarbeitung mehr oder weniger große Anteile an n-Paraffinen und Asphaltenen, die besondere Probleme darstellen, weil sie bei Erniedrigung der Temperatur auskristallisieren bzw. agglomerieren und dadurch zur Verschlechterung der Fließeigenschaften dieser Öle führen können. Diese Verschlechterung der Fließeigenschaften der Öle bezeichnet man als "Stocken" des Öles. Der Stockpunkt ist die normierte Bezeichnung für diejenige Temperatur, bei der ein Öl, z.B. Mineralöl, Dieselkraftstoff oder Hydraulikflüssigkeit bei Abkühlung gerade eben zu fließen aufhört. Der Stockpunkt (Pour Point) ist jedoch nicht identisch mit dem sogenannten Fließpunkt. Der Fließpunkt ist eine unspezifische, nicht durch Normen abgedeckte Bezeichnung für diejenige Temperatur, bei der ein Feststoff unter gegebenen Messbedingungen zu fließen beginnt. Durch die Verschlechterung der Fließeigenschaften können dann beispielsweise beim Transport, bei der Lagerung und/oder der Verarbeitung dieser Öle Behälter, Rohrleitungen, Ventile oder Pumpen verstopfen, insbesondere bei paraffinhaltigen Ölen, die schwierig zu inhibieren sind. Darüber hinaus erfordern Paraffinausfällungen erhöhte Drücke beim Wiederanfahren von Pipelines (Yield Point). Crude oils, residual oils, oil distillates, e.g. Diesel fuel, mineral oils, Lubricating oils, hydraulic oils, etc. contain depending on their origin or the nature of their Processing more or less large amounts of n-paraffins and asphaltenes, which pose particular problems because they decrease in temperature crystallize out or agglomerate and thereby deteriorate the Flow properties of these oils can lead. This deterioration in The flow properties of the oils are known as "stagnation" of the oil. The Pour point is the standardized name for the temperature at which an oil, e.g. Mineral oil, diesel fuel or hydraulic fluid when cooling down just stops flowing. However, the pour point is not identical to the so-called pour point. The pour point is non-specific, not by Standard-covered term for the temperature at which a solid begins to flow under given measuring conditions. Through the The flow properties can then deteriorate, for example, when Transportation, storage and / or processing of these oils containers, Pipes, valves or pumps are blocked, especially if they contain paraffin Oils that are difficult to inhibit. Also require Paraffin precipitation increased pressures when restarting pipelines (Yield Point).
Besondere Schwierigkeiten treten in der Praxis dann auf, wenn die Wax Appearance Temperature (WAT) und insbesondere der Eigenstockpunkt dieser Öle oberhalb der Umgebungstemperatur, insbesondere bei 20°C oder darüber liegen. In Anbetracht der abnehmenden Welterdölvorräte und zunehmender Erschließung von Lagerstätten, die Rohöle mit hohen Eigenstockpunkten liefern, erlangen die Förderung und der Transport derartiger Problemöle eine immer größer werdende Bedeutung.In practice, special difficulties arise when the wax Appearance Temperature (WAT) and in particular the intrinsic point of this Oils above ambient temperature, especially at 20 ° C or above lie. In view of the decreasing world oil reserves and increasing Development of deposits that deliver crude oils with high own stockpoints, the extraction and transportation of such problem oils always get one growing importance.
Zur Wiederherstellung oder Aufrechterhaltung der Fließfähigkeit gibt es eine Reihe von Maßnahmen thermischer oder mechanischer Art, z.B. das Abkratzen des kristallisierten Paraffins von der Rohrinnenwand durch regelmäßiges Molchen, das Beheizen ganzer Pipelines oder Spülvorgänge mit Lösungsmitteln. Eleganter ist sicherlich die ursächliche Bekämpfung des Phänomens durch Zugabe von Fließverbesserern, die auch als Stockpunkterniedriger (Pour Point Depressants) oder Paraffininhibitoren bezeichnet werden. Dabei ist im allgemeinen eine Erniedrigung des Stockpunkts auf Werte unterhalb der jeweiligen Umgebungstemperatur, insbesondere auf Werte von etwa 10°C und darunter vorteilhaft.There is one to restore or maintain fluidity Series of measures of thermal or mechanical nature, e.g. the scraping of the crystallized paraffin from the inner tube wall by regular Newts, the heating of entire pipelines or flushing processes with solvents. The cause of the phenomenon is certainly more elegant Addition of flow improvers, which are also used as pour point depressants (pour point Depressants) or paraffin inhibitors. It is in generally a lowering of the pour point to values below the respective ambient temperature, in particular to values of approximately 10 ° C. and including advantageous.
Die Wirkungsweise dieser Fließverbesserer wird im allgemeinen dadurch erklärt, dass sie die Kristallisation von Paraffinen und Asphaltenen inhibieren bzw. mit den Paraffinen oder Paraffin-Asphalten-Addukten cokristallisieren und dadurch zur Bildung kleinerer Paraffinkristalle führen, die nicht mehr aggregieren und kein die Fließfähigkeit beeinträchtigendes Netzwerk aufbauen können. Die Folge ist eine Absenkung des Stockpunktes und die Aufrechterhaltung der Fließfähigkeit des Öls bei niedriger Temperatur. Die Wirksamkeit der Fließverbesserer hängt dabei sowohl von ihrem chemischen Aufbau (Zusammensetzung) als auch von ihrer Konzentration ab.The operation of these flow improvers is generally explained by that they inhibit the crystallization of paraffins and asphaltenes or with the Co-crystallize paraffins or paraffin-asphaltene adducts and thereby to Formation of smaller wax crystals that no longer aggregate and no longer Can build flow impairing network. The consequence is one Lowering the pour point and maintaining the fluidity of the Oil at low temperature. The effectiveness of the flow improver depends on it both of their chemical structure (composition) and of their Concentration.
US-3 567 597 beschreibt Rohöle, Schieferöle und Rückstandsöle enthaltende Mineralöldestillate, die als Pour Point Depressants ein Copolymer aus Ethylen und einem Vinylester einer gesättigten aliphatischen C1 bis C30-Monocarbonsäure enthalten, wobei das Copolymer ein mittleres Molekulargewicht von 4.000 bis 60.000 hat und 40 bis 95 Gew.-% Ethylen enthält.US-3,567,597 describes mineral oil distillates containing crude oils, shale oils and residual oils which, as pour point depressants, contain a copolymer of ethylene and a vinyl ester of a saturated aliphatic C 1 to C 30 monocarboxylic acid, the copolymer having an average molecular weight of 4,000 to 60,000 and Contains 40 to 95 wt .-% ethylene.
DE-A-20 57 168 offenbart ein Verfahren zur Verringerung des Reibungsflusses in durch Leitungen strömenden öligen Flüssigkeiten und einen in geringen Konzentrationen wirksamen, scherfesten Zusatzstoff, mit dem sich die Reibungsverluste in öligen Flüssigkeiten verringern lassen. Dazu wird den Flüssigkeiten eine kleine Menge mindestens eines hochmolekularen Polymeren zugesetzt, das sich von mindestens einem α-Olefin mit 6 bis 20 C-Atomen ableitet (Polyolefin).DE-A-20 57 168 discloses a method for reducing the flow of friction in oily liquids flowing through lines and a small amount Concentrations of effective, shear-resistant additive with which the Reduce friction losses in oily liquids. This is the Liquids a small amount of at least one high molecular weight polymer added, which is derived from at least one α-olefin having 6 to 20 carbon atoms (Polyolefin).
EP-A-0 176 641 offenbart, dass sich die Eigenschaften von Poly-α-olefinen als Strömungsbeschleuniger für flüssige Kohlenwasserstoffe dadurch verbessern lassen, dass man die Polymerisation der α-Olefine nach dem Ziegler-Verfahren in Gegenwart eines Dialkylaluminiumhalogenids und einer Trialkylaluminiumverbindung durchführt.EP-A-0 176 641 discloses that the properties of poly-α-olefins are known as This will improve flow accelerators for liquid hydrocarbons leave that the polymerization of the α-olefins by the Ziegler method in Presence of a dialkyl aluminum halide and one Trialkylaluminum compound performs.
GB-A-2 305 437 offenbart Pour Point Depressanten für Rohöle. Diese umfassen ein Reaktionsprodukt aus einem Alkylphenol mit durchschnittlich mehr als 30 C-Atomen im Alkylrest, mit einem Aldehyd mit 1 bis 12 C-Atomen. Diese Pour Point Depressanten sind zur Behandlung von Rohölen geeignet, die einen Pour Point von über 4°C aufweisen.GB-A-2 305 437 discloses pour point depressants for crude oils. These include a reaction product from an alkylphenol with an average of more than 30 carbon atoms in the alkyl radical, with an aldehyde with 1 to 12 carbon atoms. This pour point Depressants are suitable for treating crude oils that have a pour point above 4 ° C.
EP-A-0 311 452 offenbart Additive zur Verbesserung des Kaltfließverhaltens von Brenn- und Schmierölen. Diese Additive umfassen ein Alkylphenol-Aldehydharz mit einem Molekulargewicht von mindestens 3000, das 6 bis 50 Kohlenstoffatome im Alkylrest aufweist und eine spezifizierte Verteilung der Kohlenstoffkettenlängen der Alkylreste zeigt.EP-A-0 311 452 discloses additives for improving the cold flow behavior of Fuel and lubricating oils. These additives include an alkylphenol aldehyde resin with a molecular weight of at least 3000, which has 6 to 50 carbon atoms in the alkyl radical and has a specified distribution of the carbon chain lengths the alkyl residue shows.
US-3 735 770 offenbart ein Verfahren zur Verbesserung der Fließfähigkeit von Rohölen in der Kälte. Dieses Verfahren umfasst die Zugabe von Copolymeren aus Ethylen mit ungesättigten Carbonsäureestern, oder von Alkylphenolen zum Öl.US 3,735,770 discloses a method for improving the flowability of Crude oils in the cold. This process involves the addition of copolymers Ethylene with unsaturated carboxylic acid esters, or from alkylphenols to oil.
EP-A-0 857 776 offenbart Mischungen aus Ethylen-Copolymeren, Alkylphenol-Formaldehydharzen und gegebenenfalls Paraffindispergatoren (polaren stickstoffhaltigen Verbindungen) zur Verbesserung der Kälteeigenschaften von Mineralölen. Diese Mischungen zeigen in paraffinreichen Rohölen mit langkettigen Paraffinen jedoch keine ausreichende Wirksamkeit.EP-A-0 857 776 discloses mixtures of ethylene copolymers, alkylphenol-formaldehyde resins and optionally paraffin dispersants (polar nitrogenous compounds) to improve the cold properties of Mineral oils. These blends show up in paraffin-rich crude oils with long chain However, paraffins are not sufficiently effective.
Nachteilig bei den bekannten Fließverbesserern für Roh- und Rückstandsöle sind die in vielen Fällen noch nicht ausreichende Wirksamkeit und die daraus resultierenden hohen Einsatzkonzentrationen, insbesondere bei Ölen mit hohem Anteil an langkettigen n-Paraffinen mit mehr als 30 Kohlenstoffatomen. Die bekannten Fließverbesserer begünstigen darüber hinaus durch Absenkung der Viskosität des additivierten Öls die Sedimentation der ausgefallenen, spezifisch schwereren Paraffinkristalle. Hochmolekulare Poly-α-Olefine vermögen zwar das Strömungsverhalten von Ölen zu verbessern, doch verbessern sie nicht deren Kälteverhalten. Weiterhin nachteilig sind die hohen Eigenstockpunkte der Fließverbesserer, die für die Dosierung eine Erwärmung und/oder eine sehr starke Verdünnung erfordern.A disadvantage of the known flow improvers for crude and residue oils in many cases still insufficient effectiveness and the resulting resulting high use concentrations, especially with oils with high Proportion of long-chain n-paraffins with more than 30 carbon atoms. The known flow improvers also favor by lowering the Viscosity of the additive oil the sedimentation of the failed, specific heavier wax crystals. High-molecular poly-α-olefins can do that To improve the flow behavior of oils, but they do not improve them Low-temperature behavior. The high intrinsic storey points of the Flow improvers that are used for dosing a warming and / or a very strong one Require dilution.
Es werden deshalb Additive gesucht, die verbesserte Eigenschaften als Stockpunkterniedriger aufweisen, d.h. die auch bei geringer Dosierung noch genügende Wirksamkeit besitzen und im Vergleich mit Stockpunkterniedrigern des Standes der Technik bei gleich hoher Konzentration einen niedrigeren Eigenstockpunkt haben und bei einer Vielzahl von Ölen, insbesondere bei paraffinhaltigen Ölen wirksam sind. Das Additiv soll den Cloud Point herabsetzen, die Viskosität und den Yield Point des Öls in der Kälte reduzieren, und die Sedimentation der ausgefallenen Paraffinkristalle verzögern oder unterbinden.Additives are therefore sought which have improved properties as Pour point lower, i.e. which even with low doses have sufficient effectiveness and in comparison with pour point depressants of the prior art with a lower concentration Have their own pour point and with a variety of oils, especially at paraffinic oils are effective. The additive is supposed to lower the cloud point, reduce the viscosity and yield point of the oil in the cold, and the Delay or prevent sedimentation of the failed paraffin crystals.
Überraschenderweise wurde nun gefunden, dass mit einer ternären Mischung von Wirkstoffen die geforderten Eigenschaften des Additivs zu erreichen sind.Surprisingly, it has now been found that with a ternary mixture of Active ingredients the required properties of the additive can be achieved.
Gegenstand der Erfindung sind somit Additive zur Verbesserung der Fließfähigkeit
von Mineralölen, enthaltend
Ein weiterer Gegenstand der Erfindung sind Mineralöle, die die beschriebenen Mischungen aus den Bestandteilen A), B),und C) enthalten.Another object of the invention are mineral oils that described Contain mixtures of the components A), B), and C).
Ein weiterer Gegenstand der Erfindung ist die Verwendung dieser Zusammensetzung zur Verbesserung der Kaltfließeigenschaften und Lagerstabilität von Mineralölen.Another object of the invention is the use of these Composition to improve cold flow properties and Storage stability of mineral oils.
Bevorzugt enthalten die erfindungsgemäßen Mischungen 2 bis 30 Gew.-%, speziell 5 bis 25 Gew.-% Copolymer A), 25 bis 70 Gew.-%, speziell 30 bis 60 Gew.-% Poly-α-Olefin B) und 5 bis 65 Gew.-%, speziell 10 bis 50 Gew.-% organische Säure C).The mixtures according to the invention preferably contain 2 to 30% by weight, especially 5 to 25% by weight of copolymer A), 25 to 70% by weight, especially 30 to 60 % By weight poly-α-olefin B) and 5 to 65% by weight, especially 10 to 50% by weight organic acid C).
Bei den Vinylestern des Bestandteils A1) handelt es sich im allgemeinen um
solche der Formel 2
Bei den Acrylestern des Bestandteils A1) handelt es sich vorzugsweise um solche
der Formel 3
Die Copolymere des Bestandteils A1) können neben Vinyl- und/oder
(Meth)Acrylestern der Formeln 2 und 3 auch bis zu 5 mol-% Struktureinheiten von
Alkylvinylethern und/oder Olefinen umfassen.
Bei den Alkylvinylethern handelt es sich vorzugsweise um Verbindungen der
Formel 4
The alkyl vinyl ethers are preferably compounds of the formula 4
Bei den Olefinen handelt es sich vorzugsweise um Alkene mit 3 bis 30, insbesondere mit 3 bis 10 Kohlenstoffatomen. Geeignete Olefine sind beispielsweise Propen, Buten, Isobuten, Penten, Hexen, Isohexen, Diisobutylen und Norbornen.The olefins are preferably alkenes with 3 to 30, especially with 3 to 10 carbon atoms. Suitable olefins are for example propene, butene, isobutene, pentene, hexene, isohexene, diisobutylene and norbornene.
Die Alkylreste R4, R6 und R7 können in untergeordneten Mengen funktionelle Gruppen wie z.B. Amino-, Amido-, Nitro-, Cyano-, Hydroxy-, Keto-, Carbonyl-, Carboxy-, Ester-, Sulfogruppen oder Halogenatome tragen, solange diese den Kohlenwasserstoffcharakter der genannten Reste nicht wesentlich beeinträchtigen.The alkyl radicals R 4 , R 6 and R 7 can carry minor amounts of functional groups such as amino, amido, nitro, cyano, hydroxyl, keto, carbonyl, carboxy, ester, sulfo groups or halogen atoms, as long as these do not significantly impair the hydrocarbon character of the radicals mentioned.
Das Molekulargewicht der Copolymere des Bestandteils A1) liegt vorzugsweise zwischen 1000 und 100.000 Einheiten, was gemäß DIN 53735 bei 190°C und einer Auflagekraft von 2,16 kg gemessenen MFI-Werten zwischen 0,1 und 1000g/10 min entspricht.The molecular weight of the copolymers of component A1) is preferably between 1000 and 100,000 units, which according to DIN 53735 at 190 ° C and a tracking force of 2.16 kg measured MFI values between 0.1 and Corresponds to 1000g / 10 min.
Der Ethylengehalt in Copolymer A1) liegt zwischen 80 und 96,5, bevorzugt
zwischen 84 und 95 mol-%. Beim Bestandteil A1) handelt es sich bevorzugt um
höhermolekulare Varianten sogenannter Fließverbesserer, die Mitteldestillaten
vielfach zur Verbesserung der Kaltfließeigenschaften zugesetzt werden. Im
allgemeinen sind als Copolymer A) alle bekannten Co- bzw. Terpolymere und
deren Mischungen einsetzbar, die für sich alleine genommen die
Kaltfließeigenschaften von Mineralölen bzw. Mineralöldestillaten verbessern. Als
geeignete Co- bzw. Terpolymere sind beispielsweise zu nennen:
Insbesondere sind hier Ethylen/ Vinylacetat-, Ethylen/Vinylpropionat-, Ethylen/Versaticsäurevinylester-, Ethylen/Vinylacetat/Versaticsäurevinylester-, Ethylen/Vinylacetat/Diisobutylen-, Ethylen/Vinylacetat/4-Methylpenten- und Ethylen/Vinylacetat/Isobutylen-Copolymere zu nennen.In particular, here are ethylene / vinyl acetate, ethylene / vinyl propionate, Ethylene / versatic acid vinyl ester, ethylene / vinyl acetate / versatic acid vinyl ester, Ethylene / vinyl acetate / diisobutylene, ethylene / vinyl acetate / 4-methylpentene and To name ethylene / vinyl acetate / isobutylene copolymers.
Die Herstellung der Copolymere A1) erfolgt nach bekannten Verfahren (vgl. hierzu z.B. Ullmanns Encyclopädie der Technischen Chemie, 5. Auflage, Vol. A 21, Seiten 305 bis 413 ). Geeignet sind die Polymerisation in Lösung, in Suspension, in der Gasphase und die Hochdruckmassepolymerisation. Vorzugsweise wendet man die Hochdruckmassepolymerisation an, die bei Drücken von 50 bis 400 MPa, vorzugsweise 100 bis 300 MPa und Temperaturen von 50 bis 350°C, vorzugsweise 100 bis 300°C, durchgeführt wird. Die Reaktion der Comonomeren wird durch Radikale bildende Initiatoren (Radikalkettenstarter) eingeleitet. Zu dieser Substanzklasse gehören z.B. Sauerstoff, Hydroperoxide, Peroxide und Azoverbindungen wie Cumolhydroperoxid, t-Butylhydroperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(2-ethylhexyl)-peroxidicarbonat, t-Butylpermaleinat, t-Butylperbenzoat, Dicumylperoxid, t-Butylcumylperoxid, Di-(t-butyl)peroxid, 2,2'-Azo-bis(2-methylpropanonitril), 2,2'-Azo-bis(2-methylbutyronitril). Die Initiatoren werden einzeln oder als Gemisch aus zwei oder mehr Substanzen in Mengen von 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, eingesetzt.The copolymers A1) are prepared by known processes (see here e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A 21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably turns the high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the comonomers is initiated by radical initiators (radical chain initiators). To this class of substances belongs e.g. Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The Initiators are used individually or as a mixture of two or more substances Amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the comonomer mixture used.
Die gewünschte Schmelzviskosität der Copolymere A1) wird bei gegebener Zusammensetzung des Comonomerengemisches durch Variation der Reaktionsparameter Druck und Temperatur und gegebenenfalls durch Zusatz von Moderatoren eingestellt. Als Moderatoren haben sich Wasserstoff, gesättigte oder ungesättigte Kohlenwasserstoffe, z.B. Propan, Aldehyde, z.B. Propionaldehyd, n-Butyraldehyd oder Isobutyraldehyd, Ketone, z.B. Aceton, Methylethylketon, Methylisobutylketon, Cyclohexanon oder Alkohole, z.B. Butanol, bewährt. In Abhängigkeit von der angestrebten Viskosität werden die Moderatoren in Mengen bis zu 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, angewandt.The desired melt viscosity of the copolymers A1) is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. Hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. In Depending on the desired viscosity, the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
Die Hochdruckmassepolymerisation wird in bekannten Hochdruckreaktoren, z.B. High pressure bulk polymerization is carried out in known high pressure reactors, e.g.
Autoklaven oder Rohrreaktoren diskontinuierlich oder kontinuierlich durchgeführt, besonders bewährt haben sich Rohrreaktoren. Lösungsmittel wie aliphatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, Benzol oder Toluol, können im Reaktionsgemisch enthalten sein, wenngleich sich die lösungsmittelfreie Arbeitsweise besonders bewährt hat. Nach einer bevorzugten Ausführungsform der Polymerisation wird das Gemisch aus den Comonomeren, dem Initiator und, sofern eingesetzt, dem Moderator, einem Rohrreaktor über den Reaktoreingang sowie über einen oder mehrere Seitenäste zugeführt. Hierbei können die Comonomerenströme unterschiedlich zusammengesetzt sein (EP-B-0 271 738).Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free working method has proven particularly successful. According to a preferred The embodiment of the polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the Reactor entrance and fed via one or more side branches. in this connection the comonomer streams can be composed differently (EP-B-0 271 738).
Bevorzugte Copolymere A2) enthalten 80-100 mol-% des wiederkehrenden Strukturelements der Formel 5 wobei R8 und R9 unabhängig voneinander für Wasserstoff, Phenyl oder eine Gruppe der Formel COOR11 stehen, R10 für Wasserstoff, Methyl oder eine Gruppe der Formel -CH2COOR11 steht und R11 für einen C10- bis C30-Alkyl- oder Alkylenrest, vorzugsweise für einen C12 bis C26-Alkyl- oder Alkylenrest steht, mit der Maßgabe, dass diese wiederkehrenden Struktureinheiten mindestens eine und höchstens zwei Carbonsäureestereinheiten in einem Strukturelement enthalten.Preferred copolymers A2) contain 80-100 mol% of the recurring structural element of the formula 5 where R 8 and R 9 independently of one another are hydrogen, phenyl or a group of the formula COOR 11 , R 10 is hydrogen, methyl or a group of the formula -CH 2 COOR 11 and R 11 is a C 10 - to C 30 - Alkyl or alkylene radical, preferably a C 12 to C 26 alkyl or alkylene radical, with the proviso that these recurring structural units contain at least one and at most two carboxylic acid ester units in one structural element.
Besonders geeignet sind Copolymere, worin R8 und R9 für Wasserstoff oder eine Gruppe der Formel COOR11 und R10 für Wasserstoff oder Methyl steht. Diese Struktureinheiten leiten sich von Estern von Monocarbonsäuren wie z.B. Acrylsäure, Methacrylsäure, Zimtsäure, bzw. von Halb- oder Diestem von Dicarbonsäuren wie z.B. Maleinsäure, Fumarsäure und Itaconsäure ab. Copolymers in which R 8 and R 9 are hydrogen or a group of the formula COOR 11 and R 10 are hydrogen or methyl are particularly suitable. These structural units are derived from esters of monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, cinnamic acid, or from semi- or diesters of dicarboxylic acids, such as, for example, maleic acid, fumaric acid and itaconic acid.
Besonders bevorzugt sind die Ester der Acrylsäure.The esters of acrylic acid are particularly preferred.
Für die Veresterung der ethylenisch ungesättigten Mono- und Dicarbonsäuren geeignete Alkohole sind solche mit 10-30 C-Atomen, insbesondere solche mit 12-26 C-Atomen wie beispielsweise 1-Decanol, 1-Dodecanol, 1-Tridecanol, Isotridecanol, 1-Tetradecanol, 1-Hexadecanol, Eicosanol, Docosanol, Tetracosanol, Hexacosanol sowie natürlich vorkommende Mischungen wie z.B. Cocosfettalkohol, Talgfettalkohol und Behenylalkohol. Die Alkohole können natürlichen wie auch synthetischen Ursprungs sein.For the esterification of ethylenically unsaturated mono- and dicarboxylic acids Suitable alcohols are those with 10-30 carbon atoms, especially those with 12-26 carbon atoms such as 1-decanol, 1-dodecanol, 1-tridecanol, Isotridecanol, 1-tetradecanol, 1-hexadecanol, eicosanol, docosanol, Tetracosanol, hexacosanol and naturally occurring mixtures such as Coconut fatty alcohol, tallow fatty alcohol and behenyl alcohol. The alcohols can be of natural as well as synthetic origin.
Die Copolymere des Bestandteils A2) können neben C10-C30-Alkylestern ungesättigter Carbonsäuren bis zu 20 mol-%, bevorzugt bis zu 10 mol-% Comonomere wie Vinylester der Formel 2, (Meth)acrylsäureester der Formel 3, Alkylvinylether der Formel 4 und/oder Olefine umfassen. Weiterhin sind insbesondere Heteroatome tragende ethylenisch ungesättigte Verbindungen wie beispielsweise Allylpolyglykole, Acrylsäurebenzylester, Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxybutylacrylat, Dimethylaminoethylacrylat, Perfluoralkylacrylat, sowie die entsprechenden Ester und Amide der Methacrylsäure, Vinylpyridin, Vinylpyrrolidon, Acrylsäure, Methacrylsäure, p-Acetoxystyrol, und Methoxyessigsäurevinylester als Comonomere in Bestandteil A2) geeignet.In addition to C 10 -C 30 alkyl esters of unsaturated carboxylic acids, the copolymers of component A2) can contain up to 20 mol%, preferably up to 10 mol%, of comonomers such as vinyl esters of the formula 2, (meth) acrylic esters of the formula 3, alkyl vinyl ethers of the formula 4 and / or olefins. Furthermore, in particular heteroatoms bearing ethylenically unsaturated compounds such as allyl polyglycols, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dimethylaminoethyl acrylate, perfluoroalkyl acrylate, and the corresponding esters and amides of methacrylic acid, vinyl pyridine, vinyl pyrrolidone, acrylic acid, methacrylic acid, p-acetoxystyrene, and vinyl methoxyacetate as comonomers in Component A2) suitable.
Allylpolyglykole können in bevorzugten Ausführungsformen der Erfindung 1 bis 50 EO- oder PO-Einheiten umfassen, und der Formel 6 entsprechen: worin
- R12
- für Wasserstoff oder Methyl steht,
- Z
- für C1-C3-Alkyl steht,
- R13
- für Wasserstoff, C1-C30-Alkyl, Cycloalkyl, Aryl oder -G(O)-R8 steht,
- R14
- für Wasserstoff, C1-C20-Alkyl steht,
- R15
- für C1-C30-Alkyl, C3-C30-Alkenyl, Cycloalkyl oder Aryl steht und
- m
- eine Zahl von 1 bis 50, vorzugsweise 1 bis 30 bedeutet.
- R 12
- represents hydrogen or methyl,
- Z
- represents C 1 -C 3 alkyl,
- R 13
- represents hydrogen, C 1 -C 30 alkyl, cycloalkyl, aryl or -G (O) -R 8 ,
- R 14
- represents hydrogen, C 1 -C 20 alkyl,
- R 15
- represents C 1 -C 30 alkyl, C 3 -C 30 alkenyl, cycloalkyl or aryl and
- m
- is a number from 1 to 50, preferably 1 to 30.
Besonders bevorzugt sind Comonomere der Formel 6, bei denen R12 und R14 für Wasserstoff und R13 für Wasserstoff oder C1-C4-Alkylgruppen und steht.Comonomers of the formula 6 in which R 12 and R 14 are hydrogen and R 13 are hydrogen or C 1 -C 4 -alkyl groups and are particularly preferred.
Die Molekulargewichte bzw. Molmassenverteilungen der erfindungsgemäßen Copolymeren sind durch einen K-Wert (gemessen nach Fikentscher in 5 %iger Lösung in Toluol) von 10 bis 100, vorzugsweise 15 bis 80 charakterisiert. Die Molekulargewichte Mw können in einem Bereich von 2.000 bis 500.000, bevorzugt 5.000 bis 300.000 liegen und beispielsweise mittels Gel-Permeationschromatographie gegen Polystyrol-Standards bestimmt werden.The molecular weights or molecular weight distributions of the invention Copolymers have a K value (measured according to Fikentscher in 5% Solution in toluene) characterized from 10 to 100, preferably 15 to 80. The Molecular weights Mw can range from 2,000 to 500,000, preferred 5,000 to 300,000 and for example by means of gel permeation chromatography against polystyrene standards.
Die Herstellung der Copolymere A2) erfolgt durch (Co)polymerisation von Estern ethylenisch ungesättigter Carbonsäuren, insbesondere (Meth)Acrylaten, gegebenenfalls mit weiteren Comonomeren nach üblichen radikalischen Polymerisationsverfahren.The copolymers A2) are prepared by (co) polymerizing esters ethylenically unsaturated carboxylic acids, especially (meth) acrylates, optionally with other comonomers according to conventional radicals Polymerization.
Ein geeignetes Herstellungsverfahren besteht darin, die Monomeren in einem organischen Lösungsmittel zu lösen und in Gegenwart eines Radikalstarters bei Temperaturen im Bereich von 30 bis 150°C zu polymerisieren. Als Lösungsmittel eignen sich aromatische Kohlenwasserstoffe, wie z. B. Toluol, Xylol, Trimethylbenzol, Dimethylnaphthalin oder Gemische dieser aromatischen Kohlenwasserstoffe. Auch handelsübliche Gemische aus aromatischen Kohlenwasserstoffe wie z.B. Solvent Naphtha oder Shellsol AB® (Hersteller: Shell) finden Verwendung. Als Lösungsmittel sind ebenfalls aliphatische Kohlenwasserstoffe geeignet. Auch alkoxylierte aliphatische Alkohole oder deren Ester wie z.B. Butylglykol finden als Lösungsmittel Verwendung, bevorzugt aber als Gemisch mit aromatischen Kohlenwasserstoffen. A suitable manufacturing process is to combine the monomers in one dissolve organic solvents and in the presence of a radical initiator Polymerize temperatures in the range of 30 to 150 ° C. As a solvent are aromatic hydrocarbons such. B. toluene, xylene, Trimethylbenzene, dimethylnaphthalene or mixtures of these aromatic Hydrocarbons. Commercially available mixtures of aromatic Hydrocarbons such as Solvent Naphtha or Shellsol AB® (manufacturer: Shell) are used. Aliphatic solvents are also suitable Suitable for hydrocarbons. Also alkoxylated aliphatic alcohols or their Esters such as Butyl glycol is used as a solvent, but is preferred as a mixture with aromatic hydrocarbons.
Als Radikalstarter werden üblicherweise gebräuchliche Starter wie Azo-bisisobutyronitril, Ester von Peroxycarbonsäuren wie z.B. t-Butyl-perpivalat und t-Butyl-per-2-ethylhexanoat oder Dibenzoylperoxid verwendet.Commonly used starters such as azo-bisisobutyronitrile, Esters of peroxycarboxylic acids such as e.g. t-butyl perpivalate and t-Butyl-per-2-ethylhexanoate or dibenzoyl peroxide is used.
Die Polymere, welche Bestandteil B bilden, sind Poly-α-Olefine, die sich von Monoolefinen mit 3,4 oder 5 Kohlenstoffatomen ableiten lassen. Besonders bevorzugte Monoolefine als Grundkörper geeigneter Polyolefine sind Propylen und Isobutylen, woraus Polypropylen und Polyisobutylen als Polyolefine entstehen. Sie können weiterhin untergeordnete Mengen, bevorzugt weniger als 10 mol-% an längerkettigen α-Olefinen mit 6 bis 50, vorzugsweise 12 bis 40 Kohlenstoffatomen enthalten. Beispiele für geeignete Olefine sind 1-Dodecen, 1-Tetradecen, 1-Tridecen, 1-Hexadecen, 1-Heptadecen, 1-Octadecen, 1-Nonadecen, 1-Eicosen, 1-Hemicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, 1-Octacosen etc. sowie deren Mischungen.The polymers which form component B are poly-α-olefins which differ from Allow monoolefins with 3.4 or 5 carbon atoms to be derived. Especially preferred mono-olefins as the base of suitable polyolefins are propylene and isobutylene, of which polypropylene and polyisobutylene as polyolefins arise. You can also use minor amounts, preferably less than 10 mol% of longer-chain α-olefins with 6 to 50, preferably 12 to 40 Contain carbon atoms. Examples of suitable olefins are 1-dodecene, 1-tetradecene, 1-tridecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-Nonadecen, 1-Eicosen, 1-Hemicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, 1-Octacoses etc. and their mixtures.
Die Polyolefine B) sind durch ionische Polymerisation zugänglich, und als Handelsprodukte erhältlich (z.B. ®Ultravis, ®Napvis, ®Hyvis, ®Glissopal) (Polyisobutene von BP, BASF mit unterschiedlichen Alkylvinylidengehalten und Molekulargewichten).The polyolefins B) are accessible by ionic polymerization, and as Commercial products available (e.g. ®Ultravis, ®Napvis, ®Hyvis, ®Glissopal) (Polyisobutenes from BP, BASF with different alkyl vinylidene contents and Molecular weights).
Die aus verschiedenen Polymerisationsverfahren resultierende Verteilung der
Olefinisomeren ist für die erfindungsgemäße Verwendung im allgemeinen von
untergeordneter Bedeutung, in speziellen Fällen haben sich jedoch Poly-α-Olefine
mit einem erhöhten Alkylvinylidengehalt von mehr als 50 mol-%, insbesondere
von mehr als 70 mol-% als vorteilhaft erwiesen.
Unter Alkylvinylidengehalt versteht man den Gehalt der Polyolefine an
Struktureinheiten mit endständigen Doppelbindungen, die auf Verbindungen der
Formel 7
zurückgehen, worin R16 oder R17 Methyl oder Ethyl bedeuten und die andere
Gruppe ein Oligomeres des C3-C5-Olefins ist. Die Zahl der Kohlenstoffatome des
Poly-α-olefins beträgt zwischen 35 und 350. In einer bevorzugten
Ausführungsform der Erfindung beträgt die Zahl der Kohlenstoffatome zwischen
45 und 250.The distribution of the olefin isomers resulting from various polymerization processes is generally of minor importance for the use according to the invention, but in special cases poly-α-olefins with an increased alkylvinylidene content of more than 50 mol%, in particular more than 70 mol% proven to be advantageous.
Alkyl vinylidene content means the content of the polyolefins in structural units with terminal double bonds which are based on compounds of the formula 7 decrease in which R 16 or R 17 is methyl or ethyl and the other group is an oligomer of the C 3 -C 5 olefin. The number of carbon atoms of the poly-α-olefin is between 35 and 350. In a preferred embodiment of the invention, the number of carbon atoms is between 45 and 250.
Bei Bestandteil C1) handelt es sich um Alkylphenol-Aldehyd-Harze. Diese sind prinzipiell bekannt und beispielsweise im Römpp Chemie Lexikon, 9. Auflage, Thieme Verlag 1988-92, Band 4, S. 3351 ff. beschrieben.Component C1) is an alkylphenol-aldehyde resin. These are known in principle and for example in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351 ff.
Die Alkylreste R1 und R2 des Alkylphenols können bei den im erfindungsgemäßen Additiv eingesetzten Alkylphenol-Aldehyd-Harzen C1) gleich oder verschieden sein und besitzen 1 bis 30, bevorzugt 4 bis 20 Kohlenstoffatome; bevorzugt handelt es sich um n-, i- und tert.-Butyl, n- und i-Pentyl, n- und i-Hexyl, n- und i-Octyl, n- und i-Nonyl, n- und i-Decyl, n- und i-Dodecyl, Tripropenyl, Tetrapropenyl und Pentapropenyl. Bevorzugt ist das Phenol monoalkyliert.The alkyl radicals R 1 and R 2 of the alkylphenol can be the same or different in the alkylphenol-aldehyde resins C1) used in the additive according to the invention and have 1 to 30, preferably 4 to 20 carbon atoms; it is preferably n-, i- and tert-butyl, n- and i-pentyl, n- and i-hexyl, n- and i-octyl, n- and i-nonyl, n- and i-decyl , n- and i-dodecyl, tripropenyl, tetrapropenyl and pentapropenyl. The phenol is preferably monoalkylated.
Der aliphatische Aldehyd im Alkylphenol-Aldehyd-Harz C1) besitzt 1 bis 4 Kohlenstoffatome und ist bevorzugt Formaldehyd. Das mittlere Molekulargewicht der Alkylphenol-Aldehyd-Harze beträgt vorzugsweise 400 - 10.000, insbesondere 400 - 5000 g/mol. Voraussetzung ist hierbei, dass die Harze öllöslich sind.The aliphatic aldehyde in the alkylphenol-aldehyde resin C1) has 1 to 4 Carbon atoms and is preferably formaldehyde. The average molecular weight the alkylphenol-aldehyde resins are preferably 400-10,000, in particular 400 - 5000 g / mol. The prerequisite here is that the resins are oil-soluble.
Die Herstellung der Alkylphenol-Aldehyd-Harze C1) erfolgt in bekannter Weise durch basische Katalyse, wobei Kondensationsprodukte vom Resoltyp entstehen, oder durch saure Katalyse, wobei Kondensationsprodukte vom Novolaktyp entstehen.The alkylphenol-aldehyde resins C1) are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acid catalysis, where novolak-type condensation products arise.
Die nach beiden Arten gewonnenen Kondensate sind als Additivbestandteil C1) geeignet. Bevorzugt ist die Kondensation in Gegenwart von sauren Katalysatoren. Zur Herstellung der Alkylphenol-Aldehyd-Harze werden ein Mono- und/oder Dialkylphenol mit 1 bis 30 C-Atomen, vorzugsweise 4 bis 20 C-Atomen je Alkylgruppe, oder Gemische hiervon und ein aliphatischer Aldehyd mit 1 bis 4 C-Atomen miteinander umgesetzt, wobei pro mol Alkylphenolverbindung etwa 0,5 - 2 mol, vorzugsweise 0,7 - 1,3 mol Aldehyd eingesetzt werden.The condensates obtained according to both types are as additive component C1) suitable. The condensation in the presence of acidic catalysts is preferred. To produce the alkylphenol-aldehyde resins, a mono- and / or Dialkylphenol with 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms each Alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 4 carbon atoms reacted with each other, about per mole of alkylphenol compound 0.5-2 mol, preferably 0.7-1.3 mol, of aldehyde can be used.
Geeignete Alkylphenole sind insbesondere C4-C20-Alkylphenole wie beispielsweise o- oder p-Kresol, n-, sek.- und tert. Butylphenol, n- und i-Pentylphenol, n- und i-Hexylphenol, n- und i-Octylphenol, n- und i-Nonylphenol, n- und i-Decylphenol, n- und 1-Dodecylphenol, Tripropenylphenol, Tetrapropenylphenol und Pentapropenylphenol. Desgleichen sind die entsprechenden dialkylierten Phenole geeignet, wobei die Alkylreste gleich oder verschieden sein können.Suitable alkylphenols are in particular C 4 -C 20 alkylphenols such as, for example, o- or p-cresol, n-, sec.- and tert. Butylphenol, n- and i-pentylphenol, n- and i-hexylphenol, n- and i-octylphenol, n- and i-nonylphenol, n- and i-decylphenol, n- and 1-dodecylphenol, tripropenylphenol, tetrapropenylphenol and pentapropenylphenol. The corresponding dialkylated phenols are likewise suitable, it being possible for the alkyl radicals to be the same or different.
Besonders geeignete Aldehyde sind Formaldehyd, Acetaldehyd und Butyraldehyd, bevorzugt ist Formaldehyd. Der Formaldehyd kann in Form von Paraformaldehyd oder in Form einer vorzugsweise 20 bis 40 gew.-%igen wässrigen Formalinlösung eingesetzt werden. Es können auch entsprechende Mengen an Trioxan verwendet werden.Particularly suitable aldehydes are formaldehyde, acetaldehyde and Butyraldehyde, formaldehyde is preferred. The formaldehyde can take the form of Paraformaldehyde or in the form of a preferably 20 to 40 wt .-% aqueous formalin solution can be used. It can also be corresponding Amounts of trioxane can be used.
Die Umsetzung von Alkylphenol und Aldehyd erfolgt üblicherweise in Gegenwart von alkalischen Katalysatoren, beispielsweise Alkalihydroxiden oder Alkylaminen, oder von sauren Katalysatoren, beispielsweise anorganischen oder organischen Säuren, wie Salzsäure, Schwefelsäure, Phosphorsäure, Sulfonsäuren, Sulfamidosäuren oder Halogenessigsäuren, und in Gegenwart eines mit Wasser ein Azeotrop bildenden organischen Lösungsmittels, beispielsweise Toluol, Xylol, höherer Aromaten oder Gemischen hiervon. Das Reaktionsgemisch wird auf eine Temperatur von 90 bis 200°C, bevorzugt 100 - 160°C erhitzt, wobei das entstehende Reaktionswasser während der Umsetzung durch azeotrope Destillation entfernt wird. Lösungsmittel, die unter den Bedingungen der Kondensation keine Protonen abspalten, können nach der Kondensationsreaktion in den Produkten bleiben. Die Harze können direkt oder nach Neutralisation des Katalysators eingesetzt werden, gegebenenfalls nach weiterer Verdünnung der Lösung mit aliphatischen und/oder aromatischen Kohlenwasserstoffen oder Kohlenwasserstoffgemischen, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder Lösungsmitteln wie ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Solvesso 250, ®Exxsol, ®ISOPAR- und Shellsol D-Typen.The reaction of alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic Acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acids, Sulfamido acids or haloacetic acids, and in the presence of one with water an azeotropic organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, which water of reaction formed during the reaction by azeotropic Distillation is removed. Solvents that are under the conditions of Condensation no protons can split off after the condensation reaction stay in the products. The resins can be used directly or after neutralization of the Catalyst are used, optionally after further dilution of the Solution with aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Solvesso 250, ®Exxsol, ®ISOPAR and Shellsol D types.
Bei Bestandteil C2) handelt es sich um organische, öllösliche Sulfonsäuren oder deren Metall- oder Ammoniumsalze, vorzugsweise Alkalimetallsalze. Bevorzugt sind aliphatische Sulfonsäuren wie Alkansulfonate mit 8 bis 30, besonders bevorzugt 10 bis 26, insbesondere 12 bis 24 C-Atomen. Die Sulfongruppe kann endständig sein, oder an eine Methylengruppe der Kohlenwasserstoffkette gebunden sein. Weiterhin bevorzugt sind aromatische Sulfonsäuren mit einem oder zwei C8- bis C30-, insbesondere C12- bis C24-Alkyl- oder Alkenylresten und 1 oder 2 aromatischen Ringen. Die Alkyl- oder Alkenylreste können linear oder verzweigt und an beliebigen Stellen des Aromaten gebunden sein. Bevorzugt stehen sie in para-Stellung zur Sulfongruppe bei mit Alkyl- oder Alkenylresten monosubstituierten Systemen und in ortho- und para-Stellung zur Sulfongruppe bei mit Alkyl- oder Alkenylresten disubstituierten Systemen. Als Beispiele seien genannt: Nonylbenzolsulfonsäure, Dodecylbenzolsulfonsäure, Nonylnaphthalinsulfonsäure, Dinonylbenzolsulfonsäure und Didodecylbenzolsulfonsäure.Constituent C2) is organic, oil-soluble sulfonic acids or their metal or ammonium salts, preferably alkali metal salts. Aliphatic sulfonic acids such as alkane sulfonates having 8 to 30, particularly preferably 10 to 26, in particular 12 to 24, carbon atoms are preferred. The sulfone group can be terminal or attached to a methylene group on the hydrocarbon chain. Aromatic sulfonic acids with one or two C 8 to C 30 , in particular C 12 to C 24 alkyl or alkenyl radicals and 1 or 2 aromatic rings are further preferred. The alkyl or alkenyl radicals can be linear or branched and can be attached at any point on the aromatic system. They are preferably in the para position to the sulfone group in systems monosubstituted with alkyl or alkenyl radicals and in the ortho and para position to the sulfone group in systems disubstituted with alkyl or alkenyl radicals. Examples include: nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, nonylnaphthalenesulfonic acid, dinonylbenzenesulfonic acid and didodecylbenzenesulfonic acid.
Öllöslich im Sinne der Erfindung heißt, dass mindestens 10 Gew.-% bevorzugt mindestens 1 Gew.-% insbesondere mindestens 0,1 Gew.-% des Additivs im zu additivierenden Mitteldestillat klar löslich wird. Diese Definition ist sinngemäß anzuwenden, wenn der Begriff öllöslich an anderer Stelle verwendet wird. Die erfindungsgemäßen Additive sind insbesondere geeignet, die Fließfähigkeit und Paraffinsedimentation von Rohölen und anderen paraffinhaltigen Mineralölen zu verbessern, deren Paraffinsedimente größere Anteile (vorzugsweise mehr als 20 Flächen-% gemäß GC, insbesondere 30 bis 60 Flächen-%, speziell 40 bis 50 Flächen-%) an n-Paraffinen mit C-Kettenlängen von 30 und mehr C-Atomen aufweisen. Diese Öle sind in der Regel durch Asphaltene und Harze dunkel gefärbt, bevorzugt sind sie jedoch durchsichtig. Weiterhin sind die erfindungsgemäßen Additive in der Lage, den Yield Point der additivierten Öle abzusenken und somit das Wiederanfahren von Pipelines zu erleichtern.Oil-soluble in the sense of the invention means that at least 10% by weight is preferred at least 1% by weight, in particular at least 0.1% by weight of the additive in addition additive middle distillate becomes clearly soluble. This definition is analogous apply if the term oil-soluble is used elsewhere. The additives according to the invention are particularly suitable, the flowability and paraffin sedimentation of crude oils and other paraffinic mineral oils to improve, whose paraffin sediments larger portions (preferably more than 20 area% according to GC, in particular 30 to 60 area%, especially 40 to 50 Area%) of n-paraffins with carbon chain lengths of 30 and more carbon atoms exhibit. These oils are usually dark due to asphaltenes and resins colored, but they are preferably transparent. Furthermore, the Additives according to the invention are able to determine the yield point of the additive oils lower and thus facilitate the restarting of pipelines.
Die erfindungsgemäßen Additivkomponenten können den Mineralölen getrennt oder in Mischung zugesetzt werden. Zur Verbesserung der Handhabbarkeit haben sich Lösungen oder Dispersionen, die 10 bis 90 Gew.-%, bevorzugt 20 bis 80 Gew.-%, der Additive bzw. der Additivkombination enthalten, besonders bewährt. Geeignete Lösungs- oder Dispersionsmittel sind aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder kommerzielle Lösungsmittelgemische wie Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol-, ®ISOPAR- und ®Shellsol D-Typen sowie aliphatische oder aromatische Alkohole, Ether und/oder Ester. Durch die Additivkombination in ihren Kaltfließeigenschaften verbesserte Mineralöle enthalten zwischen 0,001 und 1 Gew.-%, bevorzugt zwischen 0,01 und 0,5 Gew.-% der Additivkombination bezogen auf das Mineralöl. Die erfindungsgemäßen Additive bzw. die mit ihnen additivierten Öle können weitere Kälteadditive enthalten wie beispielsweise polare stickstoffhaltige Verbindungen oder Polyoxyalkylenether. Des weiteren können sie Korrosionsinhibitoren, Detergenz-Additive, Entschäumer, Demulgatoren, Asphaltendispergatoren und andere Additive enthalten. Die Zugabe dieser Additive zum Öl kann zusammen mit den erfindungsgemäßen Additivkomponenten oder separat erfolgen.The additive components according to the invention can be separated from the mineral oils or added in a mixture. Have to improve manageability solutions or dispersions containing 10 to 90 wt .-%, preferably 20 to 80 wt .-%, the additives or the additive combination contain, especially proven. Suitable solvents or dispersing agents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and ®Shellsol D types as well aliphatic or aromatic alcohols, ethers and / or esters. Through the Additive combination in its cold flow properties improved mineral oils contain between 0.001 and 1 wt .-%, preferably between 0.01 and 0.5% by weight of the additive combination based on the mineral oil. The additives according to the invention or the oils additized with them can contain other cold additives such as polar nitrogenous ones Compounds or polyoxyalkylene ethers. Furthermore, they can Corrosion inhibitors, detergent additives, defoamers, demulsifiers, Contain asphalt dispersants and other additives. The addition of this Additives to the oil can be used together with the invention Additive components or separately.
Es wurden folgende Fließverbesserer als Bestandteil A) verwendet:
Es wurden folgende Polyolefine (Polyisobutylene) als Bestandteil B) verwendet:
Es wurden folgende organischen Säuren als Bestandteil C) verwendet:
Unter Verwendung der oben definierten Bestandteile A, B und C wurden folgende
Additive hergestellt:
Der Yield Point ist ein Maß für die Kraft, die aufzuwenden ist, um das gestockte
Rohöl wieder in den Fließzustand zu versetzen ("Restartability"). Im Falle des
unbehandelten Öls muss bei -20°C eine Kraft von ca. 2,2 Pa aufgebracht werden,
während beim behandelten Rohöl (500 ppm, Beispiel 1) bei derselben Temperatur
lediglich 0,6 - 0,7 Pa erforderlich sind.
Die Viskositäten wurden im Temperaturbereich zwischen +50 und -20°C
aufgenommen. Dabei zeigen sich deutliche Unterschiede zwischen dem Blindwert
und der mit 500 ppm Additiv nach Beispiel 1 oder 6 behandelten Rohölprobe;
beispielhaft seien einige Viskositäten gegenübergestellt:
Nicht nur die Viskosität wird durch den Zusatz von Additiv gemäß Beispiel 1 oder 6 verringert, sondern es wird auch die Lage des beim unbehandelten Rohöl zu erkennenden Plateaus in vorteilhafter Art und Weise verschoben.Not only the viscosity is determined by the addition of additive according to Example 1 or 6 reduced, but it also increases the location of the untreated crude recognizing plateaus shifted in an advantageous manner.
Das bei der Abkühlung des Rohöls auftretende Viskositätsplateau ist auf die ab einer bestimmten Temperatur verstärkt auftretende Paraffinkristallisation zurückzuführen. Bei der mit 500 ppm Additiv gemäß Beispiel 1 oder 6 behandelten Probe erscheint das bei der unbehandelten Probe auftretende Plateau deutlich weniger ausgeprägt, und erst bei -9°C statt bei -5°C.The viscosity plateau occurring when the crude oil cools down to the at a certain temperature, paraffin crystallization occurs increasingly due. The one with 500 ppm additive according to Example 1 or 6 treated sample appears that which occurs in the untreated sample Plateau significantly less pronounced, and only at -9 ° C instead of -5 ° C.
Durchführung: Jeweils 50 ml des Testrohöls werden in ein sogenanntes
Torpedoglas gefüllt, auf 70°C erwärmt und mit 500 ppm der Additive (Beispiele 1
bis 6) versetzt. Anschließend werden die Ölproben auf der Schüttelmaschine
(250 strokes/min) für 5 min. geschüttelt und danach bei 21°C bzw. 0°C gelagert.
Die Auswertung erfolgt durch visuelle Beurteilung (ml Sediment/Aussehen der
Flüssigphase etc.; s. Tabelle) der Probe nach bzw. vor dem Zentrifugieren.
Nr.
(ml)
(°C)
(h)
D (%)
(Blindwert)
(2000 PM/min)
(2000 UPM /5min)
nicht zentrifugiert
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
(2000 UPM/5min)
No.
(Ml)
(° C)
(H)
D (%)
(Blank)
(2000 PM / min)
(2000 RPM / 5min)
not centrifuged
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
(2000 RPM / 5min)
Um die Überlegenheit der erfindungsgemäßen Zusammensetzungen über den
Stand der Technik aufzuzeigen wurden die Bestandteile A, B und C der
erfindungsgemäßen Zusammensetzung allein oder in Zweierkombinationen zur
Verbesserung der Kaltfließeigenschaften von Rohöl verwendet. In folgender
Tabelle werden Yield Point (YP), Viskosität (V) und Dispergierung (D) wie vorher
beschrieben für die angegebenen Zusammensetzungen dargestellt. Die
Dosiermenge an Additiv betrug immer 500 ppm.
Claims (10)
- An additive for improving the flowability of mineral oils comprisingA) from 1 to 40% by weight of at least one copolymer which is oil-soluble and is a cold-flow improver for mineral oils selected fromA1) copolymers of from 80 to 96.5 mol% of ethylene and from 3.5 to 20 mol% of vinyl esters of carboxylic acids having from 1 to 20 carbon atoms and/or (meth)acrylic esters of alcohols having from 1 to 8 carbon atoms, andA2) homo- or copolymers of esters which bear C10-C30-alkyl radicals and are esters of ethylenically unsaturated carboxylic acids comprising up to 20 mol% of further olefinically unsaturated compounds,B) from 20 to 80% by weight of at least one poly-α-olefin having a molecular weight of from 250 to 5000 which is derived from monoolefins having from 3 to 5 carbon atoms, andC) from 5 to 70% by weight of at least one organic acid selected fromC1) alkylphenol-aldehyde resins of the formula 1 where R1 and R2 are each independently H or alkyl radicals having from 1 to 30 carbon atoms, but where both radicals may not at the same time be H, n is an integer from 3 to 50 and R3 is H or an alkyl radical having from 1 to 4 carbon atoms, andC2) aliphatic and/or aromatic sulfonic acids of the formula R18-SO3H, where R18 is C6- to C40-alkyl, C6- to C40-alkenyl or an alk(en)ylaryl radical which has 1, 2, 3 or 4 aromatic rings and 1, 2, 3 or 4 alkyl or alkenyl radicals each having from 6 to 40 carbon atoms.
- The additive as claimed in claim 1, wherein component A1 is a copolymer of ethylene and vinyl acetate or vinyl propionate.
- The additive as claimed in claim 1 and/or 2, wherein component A1 is a copolymer which comprises up. to 5 mol% of structural units which are derived from alkyl vinyl ethers and/or olefins.
- The additive as claimed in one or more of claims 1 to 3, wherein from 80 to 100 mol% of component A2 consists of structural elements of the formula 5 where R8 and R9 are each independently hydrogen, phenyl or a group of the formula COOR11, R10 is hydrogen, methyl or a group of the formula -CH2COOR11 and R11 is a C10- to C30-alkyl or alkylene radical, preferably a C12-to C26-alkyl or alkylene radical, with the proviso that these repeating structural units comprise at least one and at most two carboxylic ester units in one structural element.
- The additive as claimed in one or more of claims 1 to 4, wherein component B is a polypropylene or polyisobutylene.
- The additive as claimed in one or more of claims 1 to 5, wherein component C is derived from a monoalkylated phenol having from 4 to 20 carbon atoms in the alkyl chain.
- The additive as claimed in one or more of claims 1 to 6, wherein component C has been condensed using formaldehyde.
- The additive as claimed in one or more of claims 1 to 7, wherein component C) is an alk(en)ylaryl-sulfonic acid having one or two C8- to C30-alkyl or alkenyl radicals and 1 or 2 aromatic rings, or a salt thereof.
- A mineral oil comprising from 0.001 to 1% by weight of an additive as claimed in one or more of claims 1 to 8.
- The use of an additive as claimed in one or more of claims 1 to 8 for improving the cold flow properties and the storage stability of mineral oil
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10029621 | 2000-06-15 | ||
DE2000129621 DE10029621C2 (en) | 2000-06-15 | 2000-06-15 | Additives to improve the cold flow properties and storage stability of crude oils |
DE10106146 | 2001-02-10 | ||
DE10106146A DE10106146A1 (en) | 2001-02-10 | 2001-02-10 | Additive for improving the cold flow properties and storage stability of mineral oil contains ethylene-unsaturated ester copolymer, low-mol. wt. polyolefin and alkylphenol-aldehyde resin or sulfonic acid |
PCT/EP2001/006414 WO2001096503A2 (en) | 2000-06-15 | 2001-06-06 | Additives for improving the cold flow properties and the storage stability of crude oil |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1294832A2 EP1294832A2 (en) | 2003-03-26 |
EP1294832B1 true EP1294832B1 (en) | 2004-09-08 |
Family
ID=26006105
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01957827A Expired - Lifetime EP1294832B1 (en) | 2000-06-15 | 2001-06-06 | Additives for improving the cold flow properties and the storage stability of crude oil |
Country Status (7)
Country | Link |
---|---|
US (1) | US6821933B2 (en) |
EP (1) | EP1294832B1 (en) |
AT (1) | ATE275616T1 (en) |
CA (1) | CA2412740A1 (en) |
DE (1) | DE50103554D1 (en) |
ES (1) | ES2228922T3 (en) |
WO (1) | WO2001096503A2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7851421B2 (en) * | 2004-06-11 | 2010-12-14 | Infineum International Limited | Detergent additives for lubricating oil compositions |
US7786060B2 (en) * | 2004-11-16 | 2010-08-31 | Infineum International Limited | Lubricating oil additive concentrates |
US20080306314A1 (en) * | 2005-05-26 | 2008-12-11 | The Lubrizol Corporation | Hydrocarbyl- and Hydroxy-Substituted Aromatic Condensate |
DE102005035276B4 (en) * | 2005-07-28 | 2007-10-11 | Clariant Produkte (Deutschland) Gmbh | Mineral oils with improved conductivity and cold flowability |
DE102005045133B4 (en) * | 2005-09-22 | 2008-07-03 | Clariant Produkte (Deutschland) Gmbh | Additives for crude oils |
ES2544239T3 (en) * | 2005-12-15 | 2015-08-28 | Infineum International Limited | Use of a corrosion inhibitor of a lubricating oil composition |
EP1923454A1 (en) * | 2006-11-17 | 2008-05-21 | Basf Se | Cold flow improver. |
WO2009064827A1 (en) * | 2007-11-16 | 2009-05-22 | The Lubrizol Corporation | Novel coupled hydrocarbyl-substituted phenol materials as oilfield wax inhibitors |
US9212330B2 (en) | 2012-10-31 | 2015-12-15 | Baker Hughes Incorporated | Process for reducing the viscosity of heavy residual crude oil during refining |
US20190062660A1 (en) | 2016-04-21 | 2019-02-28 | Universitaet Hamburg | Crude oil composition comprising an additive for improving the flow properties of paraffin-containing crude oil |
WO2018217889A1 (en) | 2017-05-23 | 2018-11-29 | Ecolab Usa Inc. | Injection system for controlled delivery of solid oil field chemicals |
EP3630341A1 (en) | 2017-05-23 | 2020-04-08 | Ecolab USA, Inc. | Dilution skid and injection system for solid/high viscosity liquid chemicals |
US10961475B2 (en) | 2018-03-06 | 2021-03-30 | Si Group, Inc. | Asphaltene dispersant composition |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3567579A (en) | 1968-04-15 | 1971-03-02 | Ca Atomic Energy Ltd | Nuclear reactor installation |
US3692676A (en) | 1969-12-22 | 1972-09-19 | Continental Oil Co | Method of friction loss reduction in oleaginous fluids flowing through conduits |
US3735770A (en) | 1972-02-09 | 1973-05-29 | Gulf Research Development Co | Method for increasing the mobility of waxy crude oils |
DE3476777D1 (en) | 1984-10-05 | 1989-03-23 | Pony Ind Inc | Hydrocarbon fluid friction reducing composition containing olefin copolymer and process for producing same |
DE3443475A1 (en) | 1984-11-29 | 1986-05-28 | Amoco Corp., Chicago, Ill. | TERPOLYMERISATE OF ETHYLENE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
DE3616056A1 (en) | 1985-05-29 | 1986-12-04 | Hoechst Ag, 65929 Frankfurt | USE OF ETHYLENE TERPOLYMERISATES AS ADDITIVES FOR MINERAL OILS AND MINERAL OIL DISTILLATES |
DE3625174A1 (en) | 1986-07-25 | 1988-01-28 | Ruhrchemie Ag | METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES |
DE3640613A1 (en) | 1986-11-27 | 1988-06-09 | Ruhrchemie Ag | METHOD FOR THE PRODUCTION OF ETHYLENE MIXED POLYMERISATES AND THE USE THEREOF AS AN ADDITION TO MINERAL OIL AND MINERAL OIL FRACTIONS |
US5039437A (en) | 1987-10-08 | 1991-08-13 | Exxon Chemical Patents, Inc. | Alkyl phenol-formaldehyde condensates as lubricating oil additives |
US4931164A (en) | 1988-11-14 | 1990-06-05 | Exxon Chemical Patents Inc. | Antifoulant additive for light end hydrocarbons |
IT1229656B (en) * | 1989-04-21 | 1991-09-06 | Mini Ricerca Scient Tecnolog | LUBRICANT COMPOSITIONS CONTAINING NON METALLIC DITHIOPHOSPHATES. |
DE3921279A1 (en) | 1989-06-29 | 1991-01-03 | Hoechst Ag | METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES |
DE4020640A1 (en) | 1990-06-29 | 1992-01-02 | Hoechst Ag | TERPOLYMERISATES OF ETHYLENE, THEIR PRODUCTION AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES |
US5118875A (en) * | 1990-10-10 | 1992-06-02 | Exxon Chemical Patents Inc. | Method of preparing alkyl phenol-formaldehyde condensates |
DE4040228A1 (en) | 1990-12-15 | 1992-06-17 | Hoechst Ag | METHOD FOR PRODUCING ETHYLENE ALKYLCARBONIC ACID VINYL ESTER MIXED POLYMERISIS |
DE4042206A1 (en) | 1990-12-29 | 1992-07-02 | Hoechst Ag | ETHYLENE TERPOLYMERISES, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR MINERALOLE DISTILLATES |
GB9122351D0 (en) * | 1991-10-22 | 1991-12-04 | Exxon Chemical Patents Inc | Oil and fuel oil compositions |
JPH05331481A (en) * | 1992-05-29 | 1993-12-14 | Tonen Corp | Lubricant composition for two-cycle engine |
US5707946A (en) * | 1996-04-08 | 1998-01-13 | The Lubrizol Corporation | Pour point depressants and their use |
AU701875B2 (en) | 1995-09-08 | 1999-02-11 | Lubrizol Corporation, The | Pour point depressants and their use |
DE19620119C1 (en) | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymers of ethylene, their production and their use as additives for mineral oil distillates |
DE19620118C1 (en) | 1996-05-18 | 1997-10-23 | Hoechst Ag | Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates |
DE19620116A1 (en) | 1996-05-18 | 1997-11-20 | Max Aicher Umwelttechnik Gmbh | Method and device for treating pasty or bulk material in a horizontal tube reactor |
CN1074037C (en) * | 1996-09-04 | 2001-10-31 | 中国科学院大连化学物理研究所 | Pour point reducer for high pour point crude oil |
US5741764A (en) * | 1996-10-15 | 1998-04-21 | The Lubrizol Corporation | Two-cycle lubricant containing solvent and high molecular weight polymer |
DE19645430A1 (en) * | 1996-11-04 | 1998-05-07 | Basf Ag | Polyolefins and their functionalized derivatives |
US5939365A (en) * | 1996-12-20 | 1999-08-17 | Exxon Chemical Patents Inc. | Lubricant with a higher molecular weight copolymer lube oil flow improver |
ES2183073T5 (en) * | 1997-01-07 | 2007-10-16 | Clariant Produkte (Deutschland) Gmbh | IMPROVEMENT OF THE FLUIDITY OF MINERAL AND DISTILLED OILS OF MINERAL OILS BY MEASURING USE OF RENT-PHENOLS AND ALDEHIDS RESINS. |
US6048904A (en) * | 1998-12-01 | 2000-04-11 | Exxon Research And Engineering Co. | Branched alkyl-aromatic sulfonic acid dispersants for solublizing asphaltenes in petroleum oils |
US6475963B1 (en) * | 2001-05-01 | 2002-11-05 | Infineum International Ltd. | Carboxylate-vinyl ester copolymer blend compositions for lubricating oil flow improvement |
-
2001
- 2001-06-06 AT AT01957827T patent/ATE275616T1/en not_active IP Right Cessation
- 2001-06-06 ES ES01957827T patent/ES2228922T3/en not_active Expired - Lifetime
- 2001-06-06 WO PCT/EP2001/006414 patent/WO2001096503A2/en active IP Right Grant
- 2001-06-06 EP EP01957827A patent/EP1294832B1/en not_active Expired - Lifetime
- 2001-06-06 US US10/311,057 patent/US6821933B2/en not_active Expired - Fee Related
- 2001-06-06 DE DE50103554T patent/DE50103554D1/en not_active Expired - Lifetime
- 2001-06-06 CA CA002412740A patent/CA2412740A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
ATE275616T1 (en) | 2004-09-15 |
US20030171221A1 (en) | 2003-09-11 |
CA2412740A1 (en) | 2002-12-13 |
EP1294832A2 (en) | 2003-03-26 |
WO2001096503A2 (en) | 2001-12-20 |
US6821933B2 (en) | 2004-11-23 |
DE50103554D1 (en) | 2004-10-14 |
WO2001096503A3 (en) | 2003-01-09 |
ES2228922T3 (en) | 2005-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102006061103B4 (en) | Dispersions of polymeric oil additives | |
DE10012267B4 (en) | Copolymer blends and their use as an additive to improve the cold flow properties of middle distillates | |
EP1881054B1 (en) | Additives for improving the cold properties of fuel oils | |
EP1541664B1 (en) | Fuel oils comprising middle distillates and oils of vegetable or animal origin with improved cold properties | |
EP1294832B1 (en) | Additives for improving the cold flow properties and the storage stability of crude oil | |
EP1881053B1 (en) | Additives for improving the cold properties of fuel oils | |
EP1808449B1 (en) | Additives for mineral oil destillates having a low sulphur content comprising graft copolymers based on copolymers of ethylene and vinyl esters | |
DE10260714A1 (en) | Fuel oils with improved cold properties | |
EP1808450A1 (en) | Additives for low-sulphur mineral oil distillates, including graft copolymers based on ethylene-vinyl ester copolymers | |
EP1874899A1 (en) | Turbine fuel composition exhibiting improved cold properties | |
DE19901803B4 (en) | Copolymers and their use as an additive for improving the cold flow properties of middle distillates | |
DE10155748B4 (en) | Low-sulfur mineral oil distillates having improved cold properties, comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters | |
DE10155774A1 (en) | Additives for low sulfur mineral oil distillates, comprising an ester of an alkoxylated polyol and a polar nitrogen-containing paraffin dispersant | |
DE10319028B4 (en) | Demulsifiers for mixtures of middle distillates with fuel oils of vegetable or animal origin | |
EP1134275B1 (en) | Copolymer blends and their use as additive to improve the cold flow properties of middle distillates | |
KR20180098315A (en) | Easily handled polymer composition | |
DE10155747A1 (en) | Additives for low sulfur mineral oil distillates comprising an alkoxylated polyol ester and an alkylphenol aldehyde resin | |
DE10029621C2 (en) | Additives to improve the cold flow properties and storage stability of crude oils | |
DE102006033151B4 (en) | Additives for improving the cold properties of fuel oils | |
DE10106146A1 (en) | Additive for improving the cold flow properties and storage stability of mineral oil contains ethylene-unsaturated ester copolymer, low-mol. wt. polyolefin and alkylphenol-aldehyde resin or sulfonic acid | |
EP1770150A1 (en) | Jet fuel compositions having improved cold flow properties | |
DE19739272A1 (en) | Improving the flowability of mineral oil (distillates) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
17P | Request for examination filed |
Effective date: 20030709 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT CH CY DE DK ES GB GR IE IT LI LU MC NL TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040908 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040908 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50103554 Country of ref document: DE Date of ref document: 20041014 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20041208 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20041208 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20050111 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2228922 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050606 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050606 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050606 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050630 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050630 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20050609 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20060428 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20070427 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20070607 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070607 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20090101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090101 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20090507 AND 20090513 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20130430 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20140409 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20140602 Year of fee payment: 14 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140606 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50103554 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150606 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160101 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150606 |