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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • 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

Definitions

• the present invention relates to mixtures of fatty acids and comb polymers with improved cold stability, and their use to improve the Lubricating effect of middle distillate fuel oils.
• Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further.
• the diesel fuel standard EN 590 writes in Germany currently has a maximum sulfur content of 350 ppm. In Scandinavia already comes in with fuel oils with less than 50 ppm Exceptional cases with less than 10 ppm sulfur for use.
• This Fuel oils are usually made by taking those from petroleum Fractions obtained by distillation hydrogenated refined. In the Desulphurization also removes other substances that Give fuel oils a natural lubricating effect. About these substances include polyaromatic and polar compounds.
• JP-A-Hei-11-1692 discloses fuel oil compositions comprising 0.001 to 0.5% by weight of a C 8 -C 30 fatty acid mixture containing at least 75% by weight of unsaturated fatty acids with one and two double bonds, the The ratio of monounsaturated and doubly unsaturated fatty acids is 1: 3 to 15: 1 by weight, and the fuel oil composition contains at most 0.2% by weight of sulfur and at most 40% by weight of aromatics.
• the oils can contain other additives such as antioxidants and flow improvers.
• JP-A-Hei-10-110 175 discloses additives for improving the lubricity of fuel oils.
• the additives contain a fatty acid, selected from straight-chain saturated or unsaturated C 8 -C 28 fatty acids, as well as a pour point depressant or a cold flow improver.
• the fuel oils have a maximum sulfur content of 0.05% by weight.
• the fatty acids used according to the prior art have the disadvantage that when stored at low temperatures, i.e. often at room temperature, mostly solidify at temperatures of 0 ° C at the latest at -5 ° C, or that separate crystalline components and cause handling problems. This Problem is also only partially due to dilution with organic solvents solve, since portions crystallize from these solutions or the solution gelled and froze. So they have to be strong for use as lubricity additives diluted, or held in heated storage containers and over heated Lines are dosed.
• the object underlying the present invention was to provide lubricity additives find that reduced the lubricating effect of middle distillates Improve dosing rates, but homogeneous, clear and in particular even in the cold remain fluid.
• the invention also relates to cold stabilized solutions of fatty acid mixtures according to the invention in solvents, such as e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, as well as oxygen-containing hydrocarbons, or mixtures thereof.
• solvents such as e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, as well as oxygen-containing hydrocarbons, or mixtures thereof.
• Another object of the invention are fuel oils containing in addition to one a larger proportion of middle distillate with a sulfur content of up to 0.05 wt minor portion of a cold stabilized fatty acid mixture as defined above.
• Another object of the invention is the use of the above Fatty acid mixtures from components A and B to improve the Lubrication properties of low-sulfur middle distillates with up to 0.05% by weight Sulfur content.
• Preferred fatty acids are those with 8-40 carbon atoms, especially 12 - 22 carbon atoms.
• the alkyl residues of the fatty acids consist of essentially from carbon and hydrogen. However, you can choose more Substituents such as Hydroxy, halogen, amino or nitro groups, provided these do not affect the predominant hydrocarbon character.
• Component A2) can contain one or more double bonds and more natural or synthetic origin. With polyunsaturated carboxylic acids whose double bonds can be isolated or conjugated.
• the proportion of saturated Fatty acids A1) in the mixture of A1) and A2) is preferably below 20% by weight, in particular below 10% by weight, especially below 5% by weight.
• preferred Fatty acid mixtures which here means the combination of A1) and A2) contain at least 50% by weight, in particular at least 75% by weight, especially at least 90% by weight of the components one or more Double bonds.
• These preferred fatty acids (blends) have iodine numbers of at least 40 g I / 100 g, preferably at least 80 g I / 100 g, in particular at least 125 g I / 100 g.
• Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, Palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and Erucic acid, palmitoleic, myristoleic, linoleic, linolenic, elaeosteric and Arachidonic acid, ricinoleic acid and those obtained from natural fats and oils Fatty acid mixtures, e.g. Coconut oil, peanut oil, fish, linseed oil, palm oil, Rapeseed oil, castor oil, castor oil, rapeseed oil, soybean oil, sunflower oil and tall oil fatty acid.
• Fatty acid mixtures e.g. Coconut oil, peanut oil, fish, linseed oil, palm oil, Rapeseed oil, castor oil, castor oil, rapeseed oil, soybean oil, sunflower oil and tall oil fatty acid.
• dicarboxylic acids such as dimer fatty acids and alkyl and alkenylsuccinic acids with C 8 -C 50 alk (en) yl radicals, preferably with C 8 -C 40 , in particular with C 12 -C 22 alkyl radicals.
• the alkyl radicals can be linear or branched (oligomerized alkenes, PIB).
• the fatty acids may further contain 1-40, especially 1-25% by weight of resin acids, based on the weight of A1) and A2) together.
• R 1 is preferably an alkyl radical of preferably 10 to 24, in particular 12 to 20, carbon atoms.
• Preferred alcohols R 1 -OH are, for example, 1-decanol, 1-dodecanol, 1-tridecanol, isotridecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, eicosanol, docosanol, tetracosanol, their mixtures, 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 use of alcohol mixtures for example of dodecanol and tetradecanol or tetradecanol and hexadecanol in a ratio of 1:10 to 10: 1, in particular 3: 1 to 1: 3, has proven particularly useful.
• the additive of the fatty acid to be treated can be adjusted by varying the alcohol component. For example, by adding, for example, 15% by weight of behenyl alcohol to the above-mentioned mixtures, the effectiveness in fatty acids with a higher proportion of saturated, in particular saturated, C18 and C20 fatty acids can be optimized.
• the R 1 radicals can be linear or branched, and the branching can comprise a secondary or tertiary carbon atom.
• Linear radicals R 1 are preferred. If R 1 is branched, it preferably has this branch in the 2 position. It is possible to use different R 1 radicals, ie to use mixtures of different alcohols in the preparation of the maleic, itaconic and / or fumaric esters.
• the radicals R 1 in formula B1) are alkoxyalkyl radicals of the formula - (OA) x - R 5 wherein A is a C 2 -C 4 alkylene radical, x is an integer from 1 to 100 and R 5 is a C 1 -C 30 alkyl radical.
• the (OA) unit is preferably an ethoxy or propoxy unit. If alkoxylated units for R 1 are used, this is preferably done in a mixture with those radicals R 1 which are not alkoxylated. The proportion of alkoxylated radicals R 1 preferably does not exceed 20 mol% (based on all radicals R 1 ).
• R 5 can be linear or branched. If R 5 is branched, the branch is preferably in the 2 position. R 5 is preferably linear.
• the structural units of the formula B2) are derived on the one hand from ⁇ -olefins. These ⁇ -olefins preferably have 10 to 40, in particular 12 to 26, carbon atoms. ⁇ -olefins in the C 14 -C 24 range are particularly preferred.
• the carbon chain of the ⁇ -olefins can be straight-chain or branched, preferably it is straight-chain.
• olefins examples include 1-dodecene, 1-tetradecene, 1-tridecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosen, 1-hemicosen, 1-docosen, 1-tetracosen, 1 -Hexacoses, 1-octacoses etc. and their mixtures.
• Commercially available olefin fractions such as, for example, C 20 -C 24 or C 30+ olefin, are also suitable.
• the structural units of the formula B2) are further derived from vinyl, acrylic or Methacrylic acid esters with alkyl radicals that carry 1 to 3 carbon atoms. Especially structural units B2) which differ from vinyl acetate or Derive vinyl propionate.
• the bivalent structural units mentioned under B3) are derived from polyolefins which are derived from monoolefins having 3, 4 or 5 carbon atoms.
• Particularly preferred monoolefins as the main body of the polyolefins are propylene and isobutylene, from which polypropylene and polyisobutylene are formed as polyolefins.
• the polyolefins preferably have an alkylvinylidene content of at least 50 mol%, in particular at least 70 mol%, especially at least 75%.
• the polyolefins that are not accessible to radical polymerization generally remain in the product as non-copolymerized constituents, which also has a positive effect on the solubility and effectiveness of the polymers.
• Alkyl vinylidene content means the content of structural units in the polyolefins based on compounds of the formula decrease in which R 6 or R 7 are methyl or ethyl and the other group is an oligomer of the C 3 -C 5 olefin.
• the number of carbon atoms of the polyolefin is between 35 and 350. In a preferred embodiment of the invention, the number of carbon atoms is between 45 and 250. In a further preferred embodiment of the invention, the proportion of structural units B3) is 1 to 20 mol%, in particular 2 to 15 mol%.
• the polyolefins on which the structural units B3) are based are ionic Polymerization accessible and available as commercial products (e.g. ® Ultravis, ® Napvis, ® Hyvis, ® Glissopal) (Polyisobutenes from BP, BASF with different Alkyl vinylidene contents and molecular weights).
• the average molecular weight of the copolymers B) according to the invention is in generally between 1,500 and 200,000 g / mol, in particular between 2,000 and 100,000 g / mol (GPC against polystyrene standards in THF).
• the copolymers B) according to the invention are preferably produced at Temperatures between 50 and 220 ° C, especially 100 to 190 ° C, especially 130 to 170 ° C.
• the preferred manufacturing process is solvent-free Bulk polymerization, however, it is also possible to carry out the polymerization in the presence aromatic, aliphatic or isoaliphatic aprotic solvents such as hexane, Cyclohexane, toluene, xylene or solvent mixtures such as kerosene or solvent Perform naphtha.
• the temperature can be the boiling point of the solvent or by working under negative or positive pressure can be set particularly easily.
• radical initiators Radical chain starter
• This class of substances includes e.g. Oxygen, Hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile) or 2,2'-azobis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture from two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the mono
• the copolymers can be obtained by copolymerizing olefin and / or unsaturated Ester (component B2) and optionally polyolefin (component B3) with either maleic acid, fumaric acid, itaconic acid, itaconic or maleic anhydride or maleic acid, fumaric acid, itaconic acid esters or maleic acid, Itaconimide (component B1) can be produced. Will a copolymerization carried out with acids or anhydrides, the resulting copolymer is after esterified or imidized during production.
• This esterification or imidation takes place for example by reaction with 1.5 to 2.5 mol of alcohol or 0.8 to 1.2 mol Amine per mole of anhydride at 50 to 300, in particular 120 - 250 ° C.
• the Water of reaction can be distilled off by means of an inert gas stream or by means of azeotropic distillation.
• Copolymers B) with acid numbers of are less than 50, especially less than 30, especially less than 20 mg KOH / g prefers.
• the comonomers B1 and B2 are preferably used in equimolar amounts.
• the share of Comonomers B3 is preferably between 0.5 and 10 mol%, in particular between 1 and 5 mol%.
• the mixing ratio between A and B can vary within wide limits. So even small amounts B of 100 ppm to 50,000 ppm, preferably 1,000 ppm, are effective up to 10,000 ppm, in fatty acid solutions as a cold additive for A. They can do that Prevent self-crystallization of the fatty acid, which leads to a lowering of the Cloud points and the sedimentation of crystals formed prevents and so a problem-free handling at low temperatures allows. For special problem solutions, however, from 5% to 50%, in special cases up to 90% of component B based on the amount of Be present in component A. In particular, the own pour point of the additive is reduced and the lubricity of the additive oil is improved. Accordingly, the preferred mixing ratio of A: B is between 1:10 and 1: 0.0001, especially between 1: 4 and 1: 0.0005, especially between 1: 1 and 1: 0.001.
• the fatty acid mixtures according to the invention are oils in amounts of 0.001 to 0.5 wt .-%, preferably 0.001 to 0.1 wt .-% added. You can do it as such or dissolved in solvents such as e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as e.g. Toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types.
• solvents such as e.g. aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as e.g. Toluene, xylene, ethylbenzene, decane, pentadecane, gasoline
• Oxygen-containing hydrocarbons are also suitable as solvents.
• the fatty acid mixtures even at low Temperatures of, for example, 0 ° C, sometimes below -20 ° C and in special Cases at -40 ° C and lower can be used without problems, improve the lubricity of the additive oils as well as their cold and Corrosion protection properties.
• the fatty acid mixtures according to the invention also together with one or more oil-soluble co-additives can be used, which alone Cold flow properties and / or lubricating effect of crude oils, lubricating oils or Improve fuel oils.
• oil-soluble co-additives are those containing vinyl acetate Copolymers or terpolymers of ethylene, paraffin dispersants and Alkyl phenol-aldehyde resins.
• the 10 to 40 wt .-% vinyl acetate and 60 contain up to 90 wt .-% ethylene.
• the fatty acid mixtures according to the invention are mixed with Ethylene / vinyl acetate / neononanoic acid vinyl ester terpolymers or ethylene-vinyl acetate / Neodecanoic acid vinyl ester terpolymers to improve the Flowability of mineral oils or mineral oil distillates.
• the terpolymers of Besides contain neononanoic acid vinyl ester or the neodecanoic acid vinyl ester Ethylene 10 to 35 wt .-% vinyl acetate and 1 to 25 wt .-% of the respective Neo compound.
• other preferred copolymers contain up to 35% by weight vinyl esters still 0.5 to 20% by weight olefin such as diisobutylene, 4-methylpentene or norbornene.
• the mixing ratio of the invention Fatty acid mixtures with the ethylene / vinyl acetate copolymers described above or the terpolymers of ethylene, vinyl acetate and Vinyl esters of neononanoic or neodecanoic acid are (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.
• the fatty acid mixtures according to the invention can be mixed with Paraffin dispersants are used.
• Paraffin dispersants reduce that Size of the paraffin crystals and cause the paraffin particles to fail settle, but colloidally with significantly reduced sedimentation efforts, stay dispersed. Furthermore, they increase the lubricating effect of the fatty acid mixtures according to the invention.
• amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides can be obtained (see US 4 211 534).
• reaction products containing nitrogen Polycarboxylic acids with long-chain amines are suitable (cf. EP 0597278).
• Other Paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf.
• the fatty acid mixtures according to the invention can be used together with alkylphenol resins.
• these are alkylphenol-formaldehyde resins, for example of the formula wherein R 50 for C 4 -C 50 alkyl or alkenyl, R 51 for ethoxy and / or propoxy, n stands for a number from 5 to 100 and p stands for a number from 0 to 50.
• the mixing ratio of the fatty acid mixtures according to the invention with the Paraffin dispersants and alkylphenol resins described above is (in Parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.
• the fatty acid mixtures according to the invention are suitable, the Lubricating properties of animal, vegetable, mineral or to improve synthetic fuel oils with only low dosing rates. By their improved cold properties can be stored and applied to a Heating and / or thinning can be dispensed with. They also improve at the same time the cold and corrosion protection properties of the additive oils. Furthermore, the emulsifying properties of the additive oils are reduced impaired than is the case with the lubricating additives of the prior art.
• the fatty acid mixtures according to the invention are for use in Middle distillates are particularly suitable. Middle distillates are called especially those mineral oils that are obtained by distilling crude oil and boil in the range from 120 to 450 ° C, for example kerosene, jet fuel, diesel and heating oil.
• the oils can also contain alcohols such as methanol and / or ethanol or consist of these.
• the invention Fatty acid mixtures used in such middle distillates that 0.05 wt .-% Sulfur and less, more preferably less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases less than 50 contain ppm of sulfur.
• These are generally such Middle distillates which have been subjected to hydrogenation refining and therefore only small amounts of polyaromatic and polar compounds contain, which give them a natural lubricating effect.
• the Fatty acid mixtures according to the invention are furthermore preferably used in such Middle distillates used, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. You can also use it as a Components are used in lubricating oils.
• the mixtures can be used alone or together with others Fatty acid mixtures are used, e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, Sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and Additions to lower the cloud point. Furthermore, they become successful used together with additive packages that include known ashless Contain dispersing additives, detergents, defoamers and corrosion inhibitors.
• Self-pour points (cloud point) of the fatty acid mixtures according to the invention example composition Cloud point fatty acid comb polymer solvent 1 A1 500 ppm B1 50% naphtha -35.0 ° C 2 A1 2,000 ppm B1 50% naphtha -34.0 ° C 3 A1 5,000 ppm B1 50% naphtha -34.2 ° C 4 A1 2,000 ppm B4 50% naphtha -37.0 ° C 5 A2 2,000 ppm B1 50% naphtha 0.3 ° C 6 A2 5,000 ppm B1 50% naphtha -0.9 ° C 7 A2 2,000 ppm B2 50% naphtha 1.7 ° C 8th A2 2,000 ppm B1 30% naphtha 7.6 ° C 9 A2 5,000 ppm B1 30% naphtha 6.4 ° C 10 A2 5,000 ppm B3 30% naphtha 5.0 ° C V1 A1 - 50% naphtha -27.0 ° C V
• MS is a mixture of a number of aliphatic and cyclic, non-aromatic hydrocarbons.
• the main components of MS can be found in the following table: Components of MS component Concentration range (% by weight) Di-2-ethylhexyl 10 - 25 2-ethylhexyl acid-2-ethylhexyl 10 - 25 C 16 lactones 4 - 20 2-Ethylhexylbutyrat 3 - 10 2-ethylhexanediol- (1,3) glycol mono-n-butyrate 5 - 15 2-ethylhexanol 4 - 10 C 4 to C 8 acetates 2 - 10 2-ethylhexanediol- (1,3) 2 - 5 Ethers and esters ⁇ C 20 0 - 20
• the lubricating effect of the fatty acid mixtures was carried out using an HFRR device from PCS Instruments on additive oils at 60 ° C.
• the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No.2, p.217, 1986.
• the results are given as the coefficient of friction and wear scar (WS1.4). A low coefficient of friction and a low wear scar show a good lubricating effect.
• test oil A test oil with the following characteristics was used to test the lubricating effect: Test oil 1 boiling range: 188-285 ° C density 0.810 g / cm 3 Cloud point -29 ° C sulfur content 3 ppm Wear scar 626 ⁇ m Friction 0,375
• the boiling data are determined in accordance with ASTM D-86 and the cloud point in accordance with ISO 3015.
• Wear Scar in Test Oil 1 example additive dosage Wear scar Friction 25 according to V1 200 466 0.196 26 according to V1 400 402 0.167 27 according to example 3 200 443 0.194 28 according to example 3 400 395 0.166 29 according to example 4 400 409 0.168

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• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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