WO2009092730A1 - Production de mélanges d'additifs - Google Patents

Production de mélanges d'additifs Download PDF

Info

Publication number
WO2009092730A1
WO2009092730A1 PCT/EP2009/050652 EP2009050652W WO2009092730A1 WO 2009092730 A1 WO2009092730 A1 WO 2009092730A1 EP 2009050652 W EP2009050652 W EP 2009050652W WO 2009092730 A1 WO2009092730 A1 WO 2009092730A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixing
additive
mixtures
fuel oil
mixer
Prior art date
Application number
PCT/EP2009/050652
Other languages
German (de)
English (en)
Inventor
Wolfgang Kasel
Irene Trötsch-Schaller
Peter Spang
Frank-Olaf Mähling
Andreas Daiss
Andreas Bauder
Anja Vinckier
Stefan Hirsch
Matthias Frohberger
Siegfried Willert
Peter SCHÄFFLER
Stephan Hoffmann
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to US12/863,498 priority Critical patent/US20100293842A1/en
Priority to PL09704349T priority patent/PL2235144T3/pl
Priority to ES09704349T priority patent/ES2702625T3/es
Priority to EP09704349.1A priority patent/EP2235144B1/fr
Publication of WO2009092730A1 publication Critical patent/WO2009092730A1/fr

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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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

Definitions

  • the present invention relates to a process for the preparation of additive mixtures for fuel oils by mixing at least two additive components in a dynamic mixer or in a lamination mixer. Furthermore, the present invention relates to the additive mixtures obtainable by this process and to fuel oil compositions containing such additive mixtures.
  • Paraffinic waxes containing mineral oils and crude oils show a significant deterioration in the flow properties when the temperature is lowered.
  • the reason for this lies in the crystallization of longer-chain paraffins occurring from the cloud point temperature (cloud point), which form large platelet-shaped wax crystals. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite.
  • These cold flow improvers are usually added to the mineral oils and crude oils as additive packages.
  • These additive packages usually contain, in addition to the cold-flow at least one solvent and often also other additives, for example detergent additives, dispersants, defoamers and others.
  • the composition of crude oils and mineral oils varies due to the different origins of the crude oils and the different processing conditions in the refineries, more or less tailor-made additive packages have to be provided for the individual oils. It is therefore of great economic importance to be able to provide the additive packages in a fast, flexible process with reliably reproducible results.
  • the additive packages should not only have good functional properties, such as good cold flow improving properties, but also have good handling properties, for example, be easily incorporated into the oil.
  • additive mixtures are prepared in batches, d. H.
  • One or more active ingredient components and a solvent are metered successively into a container and then mixed by stirring or pumping.
  • the disadvantage here is the long time that is needed for charging, heating and mixing.
  • the achievement of sufficient homogeneity requires, in particular when mixing active substances and solvents of different viscosity, a longer stirring or circulating over several hours to days.
  • the desired or required mixing temperature sets itself in accordance with the amounts of the components to be mixed and their temperatures and the set heating power generally only slowly. Often, for example, it deviates significantly from the mean value at the metering point of the components as well as at the heating elements, so that the temperature progression during the mixing process is difficult to reproduce.
  • rapid heating on the heating elements e.g. the vessel shell
  • significant overheating may occur, which can lead to sedimentation of the suspended active ingredients or their thermal decomposition in the subsequent storage of the additive packages.
  • E-PA-1405896 describes a continuous process for the preparation of additive mixtures for mineral oils and mineral oil distillates, in which a cold flow improver is mixed with another cold flow improver or a solvent in a static mixer at a defined temperature.
  • Static mixers are mixing systems in which the energy required for the mixing process is entered by the mixing components. They often contain fixed installations and cause a mixing of the components by exploiting their flow energy.
  • additive mixtures for fuel oils which, in addition to good functional properties (ie properties for which these additives are added to the fuel oils at all, eg cold flow-improving properties), have improved handling properties compared with additive mixtures of the prior art have, for example, a lower minimum mixing temperature (UET) and / or better filterability of the thus addi- tivated fuel oil.
  • UDT minimum mixing temperature
  • the additive mixtures should also be able to be homogeneously composed of components which have a strongly differing viscosity and / or should be present in greatly varying proportions in the mixture.
  • the minimum blending temperature is an important economic factor for blending the fuel oils with the additives, because the lower the minimum blending temperature of an additive, the less fuel oil must be heated to mix the additive homogeneously.
  • the minimum mixing temperature is therefore of particular importance for refineries which mix additives unheated into fuel oils or mix additives into unheated fuel oils. If the minimum mixing temperature of the additive is high, filter problems may occur after unheated mixing.
  • the filterability of additized fuel oils is a measure of the solubility and miscibility of the additive used in the fuel oil.
  • the filterability is determined by means of the SEDAB method described below certainly. Good filterability is obtained if the added additive is readily mixable or soluble in the fuel oil.
  • a longer storage stability is also a significant economic factor, as it allows the production of the products in stock, so that, for example, demand peaks can be met more easily or run production rounds (for individual additive compositions) longer and thus more economical, without prolonged storage, the product quality unacceptable sinks.
  • the object has been achieved by a process for the preparation of additive mixtures for fuel oils, in which at least two components of the additive mixture are mixed in a mixer selected from dynamic mixers and lamination mixers.
  • the dynamic mixers are selected from rotor mills, sprocket dispersers, in-line dispersing machines, colloid mills, corundum disk mills, scraped surface heat exchangers, mixing pumps, and ultrasonic homogenizers.
  • the dynamic mixers are particularly preferably selected from rotor-stator systems, for example under rotor mills, sprocket dispersing machines, colloid mills, corundum disk mills and mixing pumps.
  • the dynamic mixers are selected among sprocket dispersing machines and mixing pumps. Another possibility for producing particularly good mixtures is the use of lamination mixers.
  • Lamination mixers are a special form of non-dynamic mixers in which the fluid streams to be mixed are fanned into a multiplicity of thin lamellae or films, and these lamellae are then alternately combed into each other, so that very rapid mixing occurs through diffusion and secondary flows.
  • the fanning of the inflows of the pure mixture component can be done for example by means of flow dividers, which divide the inflows into lamellar layers or films of adjustable thickness.
  • flow dividers which divide the inflows into lamellar layers or films of adjustable thickness.
  • an alternating stratification of the lamellar pure substance flows is brought about at the outlet from the flow divider, which, depending on the design, can be constructed two-dimensionally in adjacent planes or as concentric annular flows.
  • diffusion then takes place a material concentration balance between the layers and thus a mixing of the components instead.
  • the mixing of the components can also take place in a plurality of mixers arranged in any order, arrangement or combination, at least one of the mixers being a dynamic mixer or a lamination mixer.
  • the other mixers may be any desired mixer shapes, for example one or more further dynamic mixers and / or lamination mixers and / or static mixers.
  • the mixers may be arranged in series or in a combined series and parallel arrangement.
  • mixing of the components preferably takes place in a single mixer.
  • the mixing of the components is preferably carried out at elevated temperature, preferably at least 30 0 C, for example at 30 to 180 0 C or 30 to 150 0 C or 30 to 100 0 C, more preferably at least 50 0 C, for example at 50 to 180 0 C or at 50 to 150 0 C or at 50 to 100 0 C, and in particular at least 70 0 C, for example at 70 to 180 0 C or at 70 to 150 0 C or at 70 to 100 0 C.
  • the various components - can have different input temperatures at the mixer.
  • the desired mixing temperature can be set both before and during the mixing process.
  • the adjustment of the temperature before the mixing process is usually carried out by bringing the components to be mixed shortly before they are fed into the mixer to the desired temperature or kept in a storage container at the desired temperature. If, during the supply, the temperature can drop, the components are usefully brought first to a higher temperature, which drops during the feeding to the desired mixing temperature.
  • the setting of the temperature during the mixing process is generally carried out via heating elements which are installed on or in the mixer, for example via a double jacket or a tube bundle.
  • the components to be mixed shortly before they are fed into the mixer to the desired temperature or kept in a storage container at the desired temperature. If, during the supply, the temperature can drop, the components are usefully brought first to a higher temperature, which drops during the feeding to the desired mixing temperature.
  • the setting of the temperature during the mixing process is generally carried out via heating elements which are installed on or in the mixer, for example via a double jacket or a tube bundle.
  • the components to be mixed shortly before they are fed into the mixer to the desired temperature or kept in a storage container at the
  • Adjusting the mixing temperature before mixing by heating the components to be mixed to the desired or a slightly higher temperature.
  • the feeding of the components into the mixer can take place by customary processes, for example by direct addition of all components in pure form or by adding suitable premixes. If premixes are used, they may be formed in a separate step or, as mentioned above, prepared in a mixer upstream of the actual (dynamic or lamination mixer).
  • the setting of a homogeneous mixture with the desired product properties in the process according to the invention generally requires at most 200 seconds, preferably at most 120 seconds, more preferably at most 60 seconds and in particular at most 45 seconds, especially at most 30 seconds. These times are the average mixing time, i. the mean residence time of the components in the mixing zone.
  • the process of the invention can be configured as a batch, semibatch or continuous process. Preferably, however, it is a continuous process.
  • the material throughput is preferably from 0.001 to 200 t / h, particularly preferably from 0.01 to 100 t / h and in particular from 1 to 100 t / h.
  • a dynamic mixer or a lamination mixer is usually supplied with the components to be mixed via suitable supply lines, the supply of the components in the mixer, as already stated, either by direct addition of all components in pure form or by adding suitable Premixes can be made.
  • the pure components are preferably brought to the desired mixing temperature or a temperature slightly above the desired mixing temperature before being introduced into the mixer. Since the mixing time / residence time in the Usually very short, in stationary continuous operation it is usually not necessary to heat the mixer. After mixing, the mixture is then discharged continuously from the mixer.
  • the method according to the invention is used for the production of CFI additive packages.
  • the at least two components of the additive mixture (i) comprise at least one cold flow improver and (ii) at least one solvent.
  • Component (i) and component (ii) are used in a weight ratio of preferably 1:99 to 99: 1, particularly preferably from 10:90 to 90:10 and in particular from 20:80 to 80:20.
  • the cold flow improvers may be any of the common cold flow improvers of the prior art. Preferably, however, the cold flow improver is selected below
  • the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters, styrene, styrene derivatives and olefins.
  • Suitable olefins are, for example, those having 3 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond.
  • the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefin) and internally.
  • ⁇ -olefins particularly preferably ⁇ -olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
  • Suitable styrene derivatives are C 1 -C 4 -alkyl-substituted styrenes, such as ⁇ -methylstyrene, 2-, 3- or 4-methylstyrene, 2-, 3- or 4-ethylstyrene, 2-, 3- or 4-propylstyrene, 4-isopropylstyrene , 2-, 3- or 4-n-butylstyrene, 4-isobutylstyro, 4-tert-butylstyrene, 2,4- or 2,6-dimethylstyrene and 2,4- or 2,6-diethylstyrene. Preferred among these are ⁇ -methylstyrene, 2-, 3- or 4-methylstyrene, 2-, 3- or 4-ethylstyrene, 2-, 3- or 4-propylstyrene, 4-isopropylstyrene , 2-, 3- or 4-n-butyl
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 -C 20 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-
  • Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position relative to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is linear.
  • alkenylcarboxylic acid esters examples include vinyl acetate, vinyl propionate, vinylbutyrate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred.
  • a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
  • the ethylenically unsaturated monomer is selected from among alkenylcarboxylic acid esters. More preferably, the ethylenically unsaturated monomer comprises vinyl acetate.
  • copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group.
  • One of the alkenylcarboxylic esters is preferably vinyl acetate.
  • copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic ester and / or styrene and / or at least one styrene derivative in copolymerized form.
  • terpolymers ie copolymers which, in addition to an alkenylcarboxylic ester, which is preferably vinyl acetate, an olefin or a (meth) acrylic ester or styrene or a styrene derivative polymerized.
  • alkenylcarboxylic ester which is preferably vinyl acetate
  • an olefin or a (meth) acrylic ester or styrene or a styrene derivative polymerized e.g., alkenylcarboxylic acid esters, (meth) acrylic acid esters and styrene derivatives.
  • the at least one ethylenically unsaturated monomer is copolymerized in the copolymer in a total amount of preferably from 1 to 30 mol%, particularly preferably from 1 to 25 mol% and in particular from 5 to 20 mol%, based on the total copolymer.
  • the copolymer (a) preferably has a number average molecular weight M n of 500 to 20,000, particularly preferably 750 to 15,000.
  • Comb polymers (b) are, for example, those described in Comb-Like Polymers, Structure and Properties, N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 117 to 253 (1974) are described. Of the described there, for example, comb polymers of the formula II are suitable
  • D is R 17 , COOR 17 , OCOR 17 , R 18 , OCOR 17 or OR 17 ,
  • E is H, CH 3 , D or R 18 ,
  • G is H or D
  • J is H, R 18 , R 18 COOR 17 'is aryl or heterocyclyl
  • K is H, COOR 18 , OCOR 18 , OR 18 or COOH
  • L is H, R 18 COOR 18 , OCOR 18 , COOH or aryl, in which
  • R 17 is a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms
  • R 18 is a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms
  • m for a mole fraction in the range of 1, 0 to 0 , 4 and n represents a mole fraction in the range of O to 0.6.
  • Preferred comb polymers are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with a Alcohol with at least 10 carbon atoms available.
  • Other preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable.
  • Comb polymers may also be polyfumarates or polymaleinates.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • Suitable polyoxyalkylenes (c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof.
  • the polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two, linear alkyl groups having from 10 to 30 carbon atoms and a polyoxyalkylene group having a molecular weight of up to 5,000.
  • the alkyl group of the polyoxyalkylene radical preferably contains from 1 to 4 carbon atoms.
  • Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US Pat. No. 4,491,455, to which reference is hereby fully made.
  • Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III
  • R 19 and R 20 are each independently R 21 , R 21 OO-, R 21 -O-CO (CH 2 ) Z - or
  • R 21 is -O-CO (CH 2 ) Z -CO-, where R 21 is linear C 1 -C 8 -alkyl, y is a number from 1 to 4, x is a number from 2 to 200, and z is a number from 1 to 4.
  • Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000.
  • Preferred polyoxyalkylenes of the formula III in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
  • Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
  • the polar nitrogen compounds (d), which are suitably oil-soluble, may be both ionic and nonionic and preferably have at least one, more preferably at least 2, substituents of the formula> NR 22 wherein R 22 is a C 8 to C 40 hydrocarbon radical.
  • the nitrogen substituents may also be quaternized, that is in cationic form.
  • An example of such nitrogen compounds are ammonium salts and / or amides or imides which are substituted by the reaction of at least one with at least one hydrocarbon radical Amines with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof are available.
  • the amines contain at least one linear Cs-C 4 O-AI kylrest.
  • Suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues.
  • Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic".
  • Suitable acids for the reaction are, for example, cyclohexane-1, 2-dicarboxylic acid, cyclohexene-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.
  • polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR 23 R 24 wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR 35 and CO, and R 23 and R 24 are a C 9 to C 40 hydrocarbon radical optionally interrupted and / or interrupted by one or more groups selected from O, S, NR 35 and CO one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 -C 4 -alkyl optionally substituted by one or more moieties selected from CO, NR 35 , O and S , interrupted, and / or substituted by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R 38 , aryl or heterocyclyl, wherein R 37 and R 38 each independently are selected from among H or Ci-C 4 alkyl; and R 36
  • A is a methylene or polymethylene group having 2 to 20 methylene units.
  • suitable radicals R 23 and R 24 are 2-hydroxyethyl, 3
  • the cyclic system can be either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems.
  • the ring system is preferably carbo- or heteroaromatic, in particular carboaromatic.
  • polycyclic ring systems examples include condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindene and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, Benzofuran, coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems, such as decalin, and three-dimensional structures, such as ⁇ -pinene, camphene, bornylene, norborane, norbornene, bicyclo-octane and bicyclooctene.
  • suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl group-containing
  • Suitable polar nitrogen compounds are e.g. Also described in DE-A-198 48 621 of DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made.
  • Preferred polar nitrogen compounds are ammonium salts and / or amides or imides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • Preferred among these are ammonium salts and / or amides or imides of succinic acid, which is substituted by a long-chain hydrocarbon radical, in particular by a polyisobutyl radical.
  • Suitable sulfocarboxylic acids / sulfonic acids or their derivatives (e) are, for example, those of the general formula IV
  • Y is SO 3 - (NR 25 3 R 26 ) + , SO 3 - (NHR 25 2 R 26 ) + , SO 3 - (NH 2 R 25 R 26 ), SO 3 - (NH 3 R 26 ) or
  • R 25 is a hydrocarbon radical
  • R 26 and R 27 are alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain, R 28 is C 2 -C 5 -alkylene,
  • a and B are alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.
  • Such sulfocarboxylic acids or sulfonic acids and their derivatives are in the
  • Suitable poly (meth) acrylic esters (f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 4 - and cis alcohols, wherein the acid groups are neutralized with hydrogenated tallow amine.
  • Suitable poly (meth) acrylates are described, for example, in WO 00/44857, to which reference is hereby fully made.
  • Suitable alkylphenol-aldehyde resins are described for example in Römpp Chemie Lexikon, 9th edition, Thieme Verlag, 1988-1992, page 3352. These are oil-soluble polycondensation products of aliphatic aldehydes having generally 1 to 4 carbon atoms, such as formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, in particular formaldehyde, with phenols containing 1 or 2, preferably 1, alkyl group having 1 to 50, preferably 1 to 20 and especially 4 to 12 carbon atoms in the ortho or para position.
  • the molecular weight of these polycondensates is generally in the range from 400 to 10,000, preferably from 400 to 5,000.
  • the at least one cold flow improver comprises at least one copolymer of ethylene with at least one further ethylenically unsaturated monomer (a).
  • a ethylenically unsaturated monomer
  • the at least one cold flow improver (i) is a copolymer of ethylene with at least one further ethylenically unsaturated monomer (a), more preferably a copolymer of ethylene with at least one alkenylcarboxylic acid ester or a copolymer of ethylene with an alkenylcarbon acid ester and a (meth) acrylic acid ester or a copolymer of ethylene with an alkenylcarboxylic ester and styrene and especially an ethylene / vinyl acetate copolymer.
  • a copolymer of ethylene with at least one further ethylenically unsaturated monomer (a) more preferably a copolymer of ethylene with at least one alkenylcarboxylic acid ester or a copolymer of ethylene with an alkenylcarbon acid ester and a (meth) acrylic acid ester or a copolymer of ethylene with an alkenylcarboxylic este
  • the at least one cold flow improver (i) is a mixture of at least one copolymer of ethylene with at least one further ethylenically unsaturated monomer (a) with at least one polar nitrogen compound (d).
  • suitable and preferred cold flow improvers (a) and (d) reference is made to the above statements.
  • the at least one solvent (ii) is a solvent for the at least one cold flow improver (i) and is preferably selected from aliphatic and aromatic hydrocarbons and mixtures thereof.
  • solvents mixtures such as are customary for fuel additive packages are used. Examples of these are 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.
  • more polar solvents e.g.
  • solubilizers Solubilisatoren
  • the at least two components to be mixed in addition to the components (i) and (ii) also comprise
  • At least one other fuel oil additive selected from detergent additives, ashless dispersants, demulsifiers, dehazers, carrier oils, cetane improvers, metal deactivators, corrosion inhibitors, antioxidants, lubricity improvers, defoamers, antistatic agents, stabilizers, colorants, perfumes and mixtures from that.
  • the detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel oil, has a number average molecular weight (Mn) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5,000.
  • Mn number average molecular weight
  • As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groupings (A), (C), (H) and (I), longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl radical, each having M n 300 to 5000, in particular 500 to 2500, especially 700 to 2300, into consideration.
  • ammonia monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used.
  • Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
  • Further preferred monoamino groups (A) -containing additives are the polyisobutene epoxides obtainable by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.
  • WO-A-96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxy-polyisobutene).
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (D) -containing additives are preferably copolymers of C 2 -C 4 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining group of the carboxyl groups reacted with alcohols or amines.
  • Such additives are known in particular from EP-A-307 815.
  • Such additives are primarily used to prevent valve seat wear and, as described in WO-A-87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulphonic acid groups or their alkali metal or alkaline earth metal salts (E) -containing additives are preferably alkali metal or alkaline earth metal salts of a sulfosuccinic acid alkyl ester, as described in particular in EP-A-639 632.
  • Such additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Polyoxy-C2-C4-alkylene (F) containing additives are preferably polyether or polyetheramines, which by reaction of C2-C6o-alkanols, C6-C3o-alkanediols, mono- or di-C2-C3o-alkylamines, Ci-C3o Alkylcyclohexanolen or Ci-C3o-Alkylphenolen with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or Butylenoxid per hydroxyl group or amino group and, in the case of Polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416.
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxyl- late and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxyl ester groups (G) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 0 C, as described in particular in DE-A-38 38 918 are described.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates,
  • Terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol Such products also meet carrier oil properties.
  • the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are more particularly described in US-A-4,849,572.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines produced groupings containing (I) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.
  • detergent additives from group (H) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular of polyisobutenylsuccinic anhydrides, with amines. It goes without saying that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives such as succinic acid halides or esters are used.
  • Particularly preferred detergent additives are polyisobutenyl-substituted succinimides, especially the imides with aliphatic polyamines.
  • Particularly preferred polyamines are diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, with tetraethylenepentamine being particularly preferred.
  • the polyisobutenyl radical has a number-average molecular weight M n of preferably 500 to 5000, more preferably 500 to 2000 and in particular about 1000.
  • detergent additives can be used alone or in combination with at least one of the aforementioned detergent additives.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Is also useful is known as a "hydrocracking oil” and obtained in the refining of mineral oil fraction (vacuum distillate cut having a boiling range of about 360-500 0 C, obtainable from at high pressure catalytically hydrogenated and isomerized and also deparaffinized natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • Examples of synthetic carrier oils are selected from: polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyethe- ramines and carboxylic esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are prepared by reacting C 2 -C 6 -alkanols, C 6 -C 50 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkylcyclohexanols or Ci-C3o-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4,877,416.
  • polyetheramines poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobute- nolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A-38 38 918.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and Isotridecanols, such as.
  • di (n- or iso-tridecyl) phthalate di (n- or iso-tridecyl) phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, Cs-C ⁇ -alkylene oxide units, such as. B. selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C ⁇ -ds-AlkvIrest.
  • Preferred examples are tridecanol and nonylphenol.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6.
  • Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.
  • suitable corrosion inhibitors are succinic esters, especially with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenolethoxylate or tert-pentylphenolethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates, such as, for example, the products NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) available under the trade name.
  • Suitable antifoams are e.g. Polyether-modified polysiloxanes such as TEPHON 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) available under the trade name.
  • Polyether-modified polysiloxanes such as TEPHON 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) available under the trade name.
  • Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators are e.g. Salicylic acid derivatives, such as N, N'-disalicylidene-1, 2-propanediamine.
  • Component (iii) is preferably selected from antioxidants, corrosion inhibitors and antistatic agents.
  • component (iii) When component (iii) is used in the process according to the invention, the individual additives are used in amounts which are customary in relation to component (i) for such packages.
  • component (iii) When component (iii) is used in the process of the invention, preferably all three components (i), (ii) and (iii) are mixed in the dynamic mixer or in the lamination mixer. Alternatively, in the process according to the invention, preferably only component (i) and component (ii) are mixed in the dynamic mixer or in the lamination mixer.
  • Component (iii) may be incorporated in the additive mixture produced according to the invention, for example by customary mixing or mixing, in the event that in the dynamic mixer or lamination mixer used according to the invention only components (i) and (ii) are mixed the finished additive package should also contain component (iii). This is useful, for example, if the mixing in of component (iii) presents no special problems and a homogeneous package can be produced by conventional mixing methods, which has no handling disadvantages.
  • fuel oils are understood as meaning liquid fuels and liquid fuels. Suitable fuel oils are gasolines and middle distillates. Middle distillates are preferably selected from diesel fuels, heating oil and turbine fuels.
  • the heating oils are, for example, low-sulfur or sulfur-rich petroleum refines or stone or lignite distillates which usually have a boiling range of 150 to 400 ° C.
  • the heating oils are preferably low-sulfur heating oils, for example those having a sulfur content of at most 0.1% by weight, preferably of at most 0.05% by weight, more preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight.
  • heating oil is especially called heating oil for domestic oil firing systems or fuel oil EL.
  • the quality requirements for such heating oils are specified, for example, in DIN 51-603-1 (cf., also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, pp. 617 et seq., To which reference is expressly made).
  • the diesel fuels are, for example, crude oil raffinates which chrine have customarily a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example 285 ° C and a maximum sulfur content of 0.001 wt .-%.
  • diesel fuels available through refining (petroleum)
  • renewable diesel fuels synthetic diesel fuels and blends of all these types of diesel fuel are also included in the concept of diesel fuels.
  • Synthetic fuels are generally understood to be petrol and diesel fuels which, according to the Fischer-Tropsch process, are produced from various primary energy sources. to be won.
  • the primary energy source is first converted to synthesis gas, which is then further reacted catalytically to the desired fuel type.
  • the type of litigation determines whether synthetic diesel fuels or synthetic gasoline fuels are obtained. If one uses coal as the primary energy source, one speaks of a CTL fuel (CTL: coal-to-liquid); If natural gas is used, the end product is called GTL fuel (GTL: gas to liquid).
  • GTL fuel gas to liquid). Biomass is the starting material, it is a BTL fuel (BTL: biomass-to-liquid).
  • Renewable fuels are fuels that are produced from renewable raw materials, especially from plants. These include vegetable oils, biodiesel, bioethanol and also the already mentioned BTL fuels. Bioethanol is mainly used in gasoline engines and thus does not belong to the regenerative diesel fuels, but is counted among the renewable gasoline fuels. Biodiesel is generally understood to mean the lower alkyl esters of vegetable oils (or animal fats), i. their C 1 -C 4 -alkyl esters, in particular their ethyl or methyl esters and especially their methyl esters. In Europe, the most widely used biodiesel is rapeseed oil methyl ester (RME).
  • RME rapeseed oil methyl ester
  • Biodiesel is obtained by the transesterification of vegetable oils, which mainly consist of glycerol esters of long-chain fatty acids, with lower alcohols (C 1 -C 4 -alcohols), in particular with methanol, but sometimes also with ethanol.
  • vegetable oils which mainly consist of glycerol esters of long-chain fatty acids, with lower alcohols (C 1 -C 4 -alcohols), in particular with methanol, but sometimes also with ethanol.
  • Preferred diesel fuels are diesel fuels obtained by refining, synthetic diesel fuels, the GTL, CTL and BTL diesel fuels, vegetable oils, biodiesel, and mixtures of these diesel fuel types.
  • Suitable turbine fuels also referred to as jet fuels, jet fuels, jet fuel, aviation fuel or turbo-fuel, are for example fuels of the designation Jet A, Jet A-1, Jet B, JP-4, JP-5, JP-7, JP -8 and JP-8 + 100.
  • Jet A and Jet A-1 are commercially available kerosene based turbine fuel specifications. The associated standards are ASTM D 1655 and DEF STAN 91-91. Jet A and Jet A-1 have their specification maximum freezing point of -40 0 C and -47 0 C.
  • Jet B is a more cut fuel based on naphtha and kerosene fractions.
  • JP-4 is equivalent to Jet B.
  • JP 4, JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels, such as those used by the Navy and Air Force. In part, these names refer to formulations which already contain additives, such as corrosion inhibitors, anti-icing agents, static dissipators, etc.
  • Preferred turbine fuels are Jet A, Jet A-1 and JP 8.
  • gasoline fuels are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. 1990, Vol. A16, p. 719 ff. Due to their composition, petrol fuels have a lower boiling point range and a lower density compared to middle distillates.
  • the gasoline fuels can be both fuels for petrol engines in passenger cars and aviation fuel (leaded petrol with an RON of 100 to 130).
  • Preferred fuel oils are middle distillates, with diesel fuels and fuel oil being preferred.
  • the diesel fuels may, as already mentioned, be refining synthetic (GTL, CTL) or regenerative diesel fuels or mixtures thereof.
  • Another object of the invention are additive mixtures which are obtainable by the method according to the invention. Reference is made to the statements made above with regard to suitable and preferred measures of the method according to the invention and the mixing components to be used and their quantitative ratios.
  • the subject of the invention is a fuel oil composition containing an inventive additive mixture.
  • the fuel oil composition typically contains the additive mixture of the invention in conventional amounts, e.g. in an amount of from 10 to 2000 ppm by weight, preferably from 20 to 1000 ppm by weight and in particular from 50 to 500 ppm by weight.
  • the use of dynamic mixers or laminating mixers in the process according to the invention gives additive mixtures which are superior to the additive mixtures prepared by conventional mixing methods in terms of their handling properties.
  • the functional properties eg cold flow-improving properties, such as CP, PP and CFPP of the fuel oils additized with the additive mixtures or intrinsic CP and PP
  • “Substantially unchanged” means that the deviation is at most 10%, preferably at most 5%, more preferably at most 3%, and most preferably at most 1% (in comparison to additive mixtures prepared by conventional mixing methods).
  • the additive mixtures according to the invention have a lower lower mixing temperature (UET), greater storage stability and / or better filterability according to the SEDAB test described below as additive mixtures prepared by conventional mixing methods.
  • at least one of these parameters is improved by at least 10% over the additive mixtures of the prior art.
  • all three parameters are improved.
  • Particularly preferred are all three parameters around less improved at least 10% compared to the additive mixtures of the prior art. If only a part of these parameters is improved, the other parameters are not or only slightly deteriorated compared to conventionally produced additive components. "Insignificant" means that the respective measured value is worse by at most 5%, preferably by at most 3%.
  • the process according to the invention makes it possible to completely and homogeneously mix components with very different viscosities or also components which are present in very different proportions in the mixture and thereby to obtain additive mixtures which are substantially more homogeneous than with conventional mixing processes prepared mixtures.
  • the process according to the invention makes it possible to prepare additive mixtures of cold flow improvers in solvents, which are typically used in fuel oil additive packages, which have excellent handling properties. Cold flow improvers are generally highly viscous waxes which can not readily be incorporated homogeneously into such solvents.
  • Additive blends of a cold flow improver and a solvent were prepared and tested for their properties.
  • a 50% polymer solution was prepared using as cold flow improver an ethylene / vinyl acetate copolymer having a vinyl acetate content of 30 wt .-% and a viscosity of 310 mm 2 / s (at 120 0 C) and Solvent naphtha was used as the solvent.
  • the temperature of the polymer supplied as well as the mixing temperature loading was in all examples at 90 0 C.
  • the polymer solution formed by indirect cooling by means of a spiral heat exchanger (length: 1, 8 m, diameter: 8 mm) in a water bath cooled before discharge from the system.
  • Example 1 - Mixer Zahnammranzdispergiermaschine the company Kinematica, type MT5000; Speed 20,000 rpm
  • the filterability and the minimum mixing temperature of the above-prepared additive mixtures in a fuel oil were determined.
  • the CFPP (CoId Filter Plugging Point) value of fuel oils additized with the additive mixtures was determined.
  • the CP value (cloud point) and the PP value (pour point) of the cold flow improvers were determined.
  • the CP value was determined according to ASTM D 2500
  • the CFPP value in the fuel oil was determined according to DIN EN 116
  • the PP value was determined according to ASTM D 97.
  • Storage stability, minimum mixing temperature (lower mixing temperature, UET) and filterability (SEDAB) were determined as described below.
  • the CFPP value was determined at 400 ppm dosage of the additive mixtures prepared above in a fuel oil with the following specification:
  • the storage stability was determined optically. For this purpose, it was examined whether a phase separation, which can also manifest itself in a cloudiness, had occurred in the period under consideration.
  • a stainless steel vacuum filtration device (SM 16201 Sartorius) with a 500 ml filter cup, a 2000 ml suction bottle and a membrane filter (order number 11304 50 N Sartorius, 50 mm diameter, 0.8 micron pore size, 30 min at 90 0 C dried and stored dry) used.
  • the fuel oil is prefiltered to remove water, dirt and coker ingredients via a pleated filter.
  • Per experiment 500 ml of the prefiltered fuel oil are filled into a 1000 ml mixing cylinder.
  • 500 ppm of the additive mixture are added and then stored at room temperature for 16 h.
  • the sample is homogenized by pivoting the mixing cylinder twice through 180 °.
  • the membrane filter is inserted into the filtration unit and with the tap closed, the pressure is set to 200 mbar.
  • the attached filter cup is filled with the homogenized sample (500 ml).
  • the tap is opened and the filtration time is determined.
  • Samples that are completely filterable within 120 s are considered uncritical. Samples that are completely filterable within 120 s are considered “PASS”; it will be the Filtration time recorded. Samples where the filtration time is more than 120 s are considered "FAIL".
  • the feltemmischtemperatur is particularly important for such refineries, mix the additives unheated in fuel oils or mix additives in unheated fuel oils. If the minimum mixing temperature of the additive is high, filter problems may occur after unheated mixing.
  • the minimum mixing temperature was determined by a modified SEDAB filtration test:
  • a stainless steel vacuum filtration device (SM 16201 Sartorius) with a 500 ml filter cup, a 2000 ml suction bottle and a membrane filter (order number 11304 50 N Sartorius, 50 mm diameter, 0.8 micron pore size, 30 min at 90 0 C dried and stored dry) used.
  • the fuel oil is prefiltered to remove water, dirt and coker ingredients via a pleated filter.
  • Per test 500 ml of the prefiltered and non-additive fuel oil are filled into a 1000 ml mixing cylinder and brought to the temperature to be tested.
  • the tempered fuel oil is mixed with the undiluted 40 0 C warm additive mixture (500 ppm) and immediately homogenized by ten slight tilting of the mixing cylinder.
  • the membrane filter is inserted into the filtration unit with the filter top and with the tap closed, the pressure is set to 200 mbar.
  • the attached filter cup is filled with the homogenized sample (500 ml).
  • the tap is opened and the filtration time is determined.
  • Samples that are completely filterable within 120 s are considered "PASS”; the filtration time at the given temperature is recorded. Samples in which the filtration time is more than 120 s are considered “FAIL”; The residual volume, which is still contained in the filter cup after 120 seconds, is determined.
  • the temperature of the fuel oil is increased by 5 0 C and the filtration time is determined again. The temperature increase by 5 0 C is repeated until the sample is completely filterable within 120 s; the filtration time is recorded at the appropriate temperature.
  • the temperature of the fuel oil is successively lowered by 5 0 C until the sample is no longer completely filterable within 120 s.
  • the minimum temperature value of 10 0 C should not be undercut.
  • IBP 206 0 C
  • FBP 343 0 C
  • 90-20 74 0 C
  • the transit time of the unadditiv elected fuel was at 10 0 C 74 s.
  • 3 FG solids content

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne un procédé permettant de produire des mélanges d'additifs pour huiles combustibles, par mélange d'au moins deux constituants additifs dans un mélangeur dynamique ou dans un mélangeur non dynamique. L'invention concerne en outre les mélanges d'additifs pouvant être obtenus au moyen dudit procédé, ainsi que des compositions combustibles qui contiennent des mélanges d'additifs de ce type.
PCT/EP2009/050652 2008-01-22 2009-01-21 Production de mélanges d'additifs WO2009092730A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US12/863,498 US20100293842A1 (en) 2008-01-22 2009-01-21 Production of additive mixtures
PL09704349T PL2235144T3 (pl) 2008-01-22 2009-01-21 Wytwarzanie mieszanin dodatków
ES09704349T ES2702625T3 (es) 2008-01-22 2009-01-21 Preparación de mezclas de aditivos
EP09704349.1A EP2235144B1 (fr) 2008-01-22 2009-01-21 Production de mélanges d'additifs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08150496.1 2008-01-22
EP08150496 2008-01-22

Publications (1)

Publication Number Publication Date
WO2009092730A1 true WO2009092730A1 (fr) 2009-07-30

Family

ID=40637251

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/050652 WO2009092730A1 (fr) 2008-01-22 2009-01-21 Production de mélanges d'additifs

Country Status (5)

Country Link
US (1) US20100293842A1 (fr)
EP (1) EP2235144B1 (fr)
ES (1) ES2702625T3 (fr)
PL (1) PL2235144T3 (fr)
WO (1) WO2009092730A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8546468B2 (en) 2008-05-02 2013-10-01 Basf Se Method and device for the continuous production of polymers by radical polymerization

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2274343A1 (fr) * 2008-05-02 2011-01-19 Basf Se Procédé et appareil pour la polymérisation en continu de monomères polymérisables par voie cationique
CN102369262B (zh) * 2009-04-07 2014-10-15 巴斯夫欧洲公司 用于在中间馏分燃料中降低浊点的极性油溶性氮化合物和油溶性脂族化合物的混合物
SG193907A1 (en) 2011-03-25 2013-11-29 Evonik Oil Additives Gmbh A composition to improve oxidation stability of fuel oils
GB201111799D0 (en) * 2011-07-08 2011-08-24 Innospec Ltd Improvements in fuels

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455663A (en) * 1973-03-27 1976-11-17 Basf Ag Process and apparatus for mixing liquid materials showing great differences in viscosity
GB2065503A (en) * 1979-11-27 1981-07-01 Secr Defence Safety fuel admixture apparatus
US4365973A (en) * 1980-12-18 1982-12-28 Union Oil Company Of California Middle distillate fuel additive
US4435309A (en) * 1981-09-18 1984-03-06 Venture Innovations, Inc. Method of liquifying waxy materials
JPS6135831A (ja) * 1984-07-28 1986-02-20 Konishiroku Photo Ind Co Ltd 高分子の溶解方法
JPS61130397A (ja) * 1984-11-30 1986-06-18 Ipponmatsu Takeshi 水と油の合成燃料製造装置およびその利用方法
GB2189251A (en) * 1986-04-19 1987-10-21 Roehm Gmbh Oil flow-improving additives
EP0448166A2 (fr) * 1990-03-21 1991-09-25 Shell Internationale Researchmaatschappij B.V. Compositions de polymère
EP0472491A1 (fr) * 1990-08-23 1992-02-26 Sulzer Chemtech AG Dispositif de mélange laminaire statique dispositif d'additionnement ainsi que l'application du dispositif de mélange et de l'additionnement
GB2308129A (en) * 1995-11-29 1997-06-18 Lubrizol Corp Pour point depressant composition
WO1998033846A1 (fr) * 1997-02-04 1998-08-06 Bp Chemicals Limited Dispersion de polymere ester
FR2786780A1 (fr) * 1998-12-08 2000-06-09 Elf Antar France Procede de preparation d'un combustible emulsionne et son dispositif de mise en oeuvre
EP1405896A1 (fr) * 2002-10-01 2004-04-07 Clariant GmbH Procédé de fabrication des compositions d'additifs pour des huiles minérales et des distillats d'huile minérale
WO2008083724A1 (fr) * 2006-12-22 2008-07-17 Clariant Finance (Bvi) Limited Dispersions d'additifs polymères d'huiles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58138791A (ja) * 1982-02-10 1983-08-17 Nippon Oil & Fats Co Ltd 燃料油用流動性向上剤
US4877416A (en) * 1987-11-18 1989-10-31 Chevron Research Company Synergistic fuel compositions
US4849572A (en) * 1987-12-22 1989-07-18 Exxon Chemical Patents Inc. Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647)
US6194472B1 (en) * 1998-04-02 2001-02-27 Akzo Nobel N.V. Petroleum hydrocarbon in water colloidal dispersion
CN102369262B (zh) * 2009-04-07 2014-10-15 巴斯夫欧洲公司 用于在中间馏分燃料中降低浊点的极性油溶性氮化合物和油溶性脂族化合物的混合物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455663A (en) * 1973-03-27 1976-11-17 Basf Ag Process and apparatus for mixing liquid materials showing great differences in viscosity
GB2065503A (en) * 1979-11-27 1981-07-01 Secr Defence Safety fuel admixture apparatus
US4365973A (en) * 1980-12-18 1982-12-28 Union Oil Company Of California Middle distillate fuel additive
US4435309A (en) * 1981-09-18 1984-03-06 Venture Innovations, Inc. Method of liquifying waxy materials
JPS6135831A (ja) * 1984-07-28 1986-02-20 Konishiroku Photo Ind Co Ltd 高分子の溶解方法
JPS61130397A (ja) * 1984-11-30 1986-06-18 Ipponmatsu Takeshi 水と油の合成燃料製造装置およびその利用方法
GB2189251A (en) * 1986-04-19 1987-10-21 Roehm Gmbh Oil flow-improving additives
EP0448166A2 (fr) * 1990-03-21 1991-09-25 Shell Internationale Researchmaatschappij B.V. Compositions de polymère
EP0472491A1 (fr) * 1990-08-23 1992-02-26 Sulzer Chemtech AG Dispositif de mélange laminaire statique dispositif d'additionnement ainsi que l'application du dispositif de mélange et de l'additionnement
GB2308129A (en) * 1995-11-29 1997-06-18 Lubrizol Corp Pour point depressant composition
WO1998033846A1 (fr) * 1997-02-04 1998-08-06 Bp Chemicals Limited Dispersion de polymere ester
FR2786780A1 (fr) * 1998-12-08 2000-06-09 Elf Antar France Procede de preparation d'un combustible emulsionne et son dispositif de mise en oeuvre
EP1405896A1 (fr) * 2002-10-01 2004-04-07 Clariant GmbH Procédé de fabrication des compositions d'additifs pour des huiles minérales et des distillats d'huile minérale
WO2008083724A1 (fr) * 2006-12-22 2008-07-17 Clariant Finance (Bvi) Limited Dispersions d'additifs polymères d'huiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198614, Derwent World Patents Index; AN 1986-090601, XP002529695 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8546468B2 (en) 2008-05-02 2013-10-01 Basf Se Method and device for the continuous production of polymers by radical polymerization
US9108172B2 (en) 2008-05-02 2015-08-18 Basf Se Method and device for the continuous production of polymers by radical polymerization

Also Published As

Publication number Publication date
PL2235144T3 (pl) 2019-04-30
US20100293842A1 (en) 2010-11-25
EP2235144B1 (fr) 2018-09-26
ES2702625T3 (es) 2019-03-04
EP2235144A1 (fr) 2010-10-06

Similar Documents

Publication Publication Date Title
EP3099768B1 (fr) Inhibiteurs de corrosion pour carburants
EP2092045B2 (fr) Agent d'amélioration de l'écoulement à froid.
EP1692196B1 (fr) Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
EP2038380B1 (fr) Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants
EP1116781B1 (fr) Additif polyfonctionnel pour huiles combustibles
EP2585498B1 (fr) Copolymère quaternisé
EP2235144B1 (fr) Production de mélanges d'additifs
EP2563822A1 (fr) Terpolymère quaternisé
WO2017009306A1 (fr) Inhibiteurs de corrosion pour carburants et lubrifiants
EP3322775B1 (fr) Utilisation de copolymères dans des moteurs à combustion interne à injection directe
EP2811007A1 (fr) Utilisation avec de l'oxyde d'alkylène et de l'acide polycarbonique à substitution hydrocarbyle d'alkylamines quaternisés comme additifs dans les carburants et lubrifiants
WO2004106471A1 (fr) Compositions de combustibles presentant de meilleures proprietes d'ecoulement a froid
EP2417229A1 (fr) Mélange de composés azotés polaires solubles dans l'huile et de composés aliphatiques solubles dans l'huile servant à abaisser le point de trouble de combustibles de distillat moyen
EP4127107B1 (fr) Compositions et procédés de dispersion des paraffines dans des huiles de combustible à faible teneur en soufre
DE212016000150U1 (de) Korrosionsinhibitoren für Kraft- und Schmierstoffe
WO2007131894A2 (fr) Compositions d'huiles combustibles résistantes au froid
DE10324102A1 (de) Brennstoffzusammensetzungen mit verbesserten Kaltfließeingenschaften
EP3940043B1 (fr) Inhibiteurs de corrosion pour carburants et lubrifiants
DE102010039039A1 (de) Verwendung von organischen Verbindungen als Kraftstoffzusatz zur Verringerung des Kraftstoffverbrauchs von Dieselmotoren
WO2004101716A1 (fr) Compositions de combustible contenant des terpolymeres a proprietes de fluidite a froid ameliorees
WO2009130308A1 (fr) Utilisation d'additifs détergents combinés à des véhicules huileux pour réduire la consommation de carburant des moteurs diesel à injection directe
DE102010001408A1 (de) Verwendung von Ketonen als Kraftstoffzusatz zur Verringerung des Kraftstoffverbrauches von Dieselmotoren

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09704349

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 12863498

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2009704349

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE