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
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • 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
  • C10L1/196—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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• the invention relates to additives for diesel fuels with a deposit-preventing effect on paraffin crystals and with improved filterability, in particular for middle distillates.
• ethylene-vinyl acetate copolymers have been used as flow improvers for middle distillates.
• EVA copolymers ethylene-vinyl acetate copolymers
• the 20% and 90% distillation points differ within a temperature range of 65-100 degrees C, and / or as a flow improver for a distillate fuel whose 90% distillation point and boiling point differ 10-20 degrees C, ie for so-called "narrow boiling distillates”
• the additive can also be a mixture of two copolymers.
• EP-A 254 284 relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer.
• the terpolymer preferably has a molecular weight Mn of 500- 10,000 and preferably contains 6 to 20 CH3 groups per 100 CH2 groups in the side chains, which do not originate from the acetate residue
• the EVA copolymer preferably has a molecular weight Mn of 500 to 10,000 and contains 2 to 10 CH3 groups 100 CH2 groups.
• Flow improvers for mineral oils and distillates are also known from DE-A 35 01 384, which contain two copolymers, namely an ethylene-vinyl acetate copolymer with 25-35% by weight vinyl acetate content and a viscosity of 200-1,500 mPa ⁇ s (at 140 degrees C) and an ethylene-propene-vinyl acetate copolymer with 25 - 35 wt .-% vinyl acetate and a viscosity of 200 - 1 500 mPa s.
• JP-B 62 119 296 (Chem. Abstr. 107, 80 830 m) describes a flow improver for fuel oils which consists, on the one hand, of a copolymer of ethylene with at least one carboxylic acid vinyl ester with a molecular weight ⁇ 1 100 and, on the other hand, of a copolymer Ethylene with a vinyl carboxylate with a molecular weight in the range 500-10,000.
• Additives with a pour-point improving effect for gasoline, kerosene and EVA-based fuel oils are also proposed in JP-B 58 194 988 (cf. Chem. Abstr. 100, 177 634u). These are additives consisting of 2 - 98% ethylene-vinyl ester copolymers and the remaining parts of ethylene-vinyl acetate copolymer, acrylic acid ester-ethylene copolymer and the like.
• Middle distillates - as is customary in the petroleum industry - are understood to mean fractions which usually include gas oils (boiling point 170-350 degrees C, in particular 225-350 degrees C TBP according to ASTM 2892), diesel fuels, aviation turbine fuels and heating oils.
• gas oils boiling point 170-350 degrees C, in particular 225-350 degrees C TBP according to ASTM 2892
• diesel fuels diesel fuels
• aviation turbine fuels heating oils.
• fractions with a boiling range above 170 degrees C, preferably above 225 degrees C cf. Winnacker-Küchler, 4th edition, vol. 6, Carl Hanser Verlag, Kunststoff 1982
• the additives according to the invention are used for "high final boiling” diesel fuels.
• the person skilled in the art generally understands this to mean diesel fuels with a boiling point> 380 degrees C, a difference between the boiling point and 90% - distillation point> 30 degrees C.
• the additives according to the invention serve as flow improvers for middle distillates which contain more than 0.5% by weight n-alkanes with chain length ⁇ C25, especially those middle distillates whose boiling point (at 760 mm pressure) is above 360 degrees C.
• component A) is in the form of a terpolymer, it is a copolymer of 20-35% by weight of vinyl acetate, 50 to 70% by weight of ethylene and 5 to 15% by weight of a third monomer, selected from the group of Olefins, especially the alkyl dienes (used per se as comonomer) represented by, for example, diisobutylene, isobutylene, or the alkenes with more than 2 carbon atoms, represented, for example, by propene.
• a third monomer selected from the group of Olefins, especially the alkyl dienes (used per se as comonomer) represented by, for example, diisobutylene, isobutylene, or the alkenes with more than 2 carbon atoms, represented, for example, by propene.
• a measured viscosity of ⁇ spec / c of 6 - 50 ml / g corresponds approximately to a molecular weight Mw of approximately 1,000-10,000.
• a melt viscosity index (MFI) of 20-1,000 corresponds approximately to a molecular weight Mw of 20,000-10 The latter, higher molecular weight ethylene-vinyl acetate copolymers correspond to the type of hot melt adhesive available on the market.
• the analytical determinations (molecular weight, etc.) for ethylene-vinyl acetate copolymers can be carried out according to Brauer et al. Chem. Techn. 24, 630-635 (1977).
• the viscosity ⁇ spec / c is determined in accordance with DIN 1342, DIN 51 562 and DIN 7745.
• the polyalkyl (meth) acrylates C) can be prepared in a manner known per se by (radical) polymerization from the known monomers of the formula I. wherein R1 is hydrogen or methyl and R2 is an optionally branched alkyl radical having 6-26, preferably 8-24, in particular 12-20, carbon atoms.
• the polyalkyl (meth) acrylates are preferably prepared by means of solution polymerization and in a special embodiment in the presence of components A) or / and B).
• Suitable solvents LM are, for example, those described above in which the monomers dissolve and which permit polymerization at elevated temperature. A boiling point of at least 50 degrees C at 760 mm should be mentioned as a guideline.
• the solvents LM therefore fall, for example, in the group of hydrocarbons such as kerosene (boiling range 180-210 degrees C), the naphthenic oils, the paraffin-based oils or the gas oils.
• the ratios are chosen so that the polymer formed to the solvent LM is in a weight ratio of 80:20 to 20:80, preferably 60:40 to 25:75.
• a weight ratio of solvent LM to polymer of 1: 1 can be given.
• the polymerization of the monomers of the formula I can be carried out as follows: In a suitable polymerization vessel equipped with a stirrer, reflux condenser and thermometer, the monomers of the formula I are heated to a temperature above 50 ° C. in the solvent. A protective gas such as nitrogen or an inert gas such as argon or helium is expediently introduced over a certain period of time, for example for one hour, and the process is continued under protective gas.
• the polymerization is initiated by free-radical initiators known per se, preferably of the lipophilic type, in particular per compounds such as butyl perpivalate, tert-butyl peroctoate.
• the initiator additive is usually in the range 0.1 to 2% by weight, based on the monomers (cf. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylitatien, Springer Verlag 1967).
• regulators for example the known sulfur regulators, in particular mercaptans such as dodecyl mercaptan, in the customary amounts of 0.5-5% by weight, based on the monomers.
• a period of about 4 to 16 hours can usually be assumed as the total polymerization time.
• the polymer can be isolated in a manner known per se, for example by precipitation, but it is expedient to set it up in such a way that it can be processed further in solution.
• the polymerization of the monomers of the formula I in the presence of the ethylene-vinyl acetate copolymers or terpolymers can in principle be carried out in the same way:
• the dissolution of the polymers A) and B) in solvents LM is advantageously supported by heating, for example, to temperatures in the range 90 ⁇ 10 degrees C. with stirring.
• the monomers of the formula I plus initiator are advantageously metered in at elevated temperature, taking into account the decomposition temperatures of the initiators used, and under a protective gas, advantageously by means of a metering pump and within a certain period of time, for example 2 ⁇ 1/2 hours.
• initiator is added again, as a reference about 5-15% of the amount already added.
• the total polymerization time can generally be set at about 4 to 16 hours.
• the additives according to the invention are generally available as relatively concentrated polymer solutions in the solvents LM.
• the polymer content in the concentrates is 20-80% by weight. They are advantageously added to the oils or fractions, the flowability or filterability of which is to be improved, in such amounts that they contain 10-1000 ppm, preferably 50 to 500 ppm, of the polymeric additions according to the present invention.
• the positive effect of the additives according to the invention is particularly pronounced when applied to middle distillates, especially middle distillates which contain more than 0.5% by weight of n-alkanes with chain lengths ⁇ 25 carbon atoms and especially those middle distillates whose boiling point is above 230 degrees at 760 mm pressure.
• One of the objectives of the present invention was to provide additives which have both wax-preventing and flow-enhancing effects, if not over the entire range of middle distillates, but for important segments thereof.
• This goal was surprisingly achieved by the polymer combination of components A), B) and optionally C) according to the invention.
• the excellent storage stability of concentrate forms of the additives according to the invention especially in the presence of component C). It is noteworthy in this context that the advantage of improved storage stability is not bought through general cuts in effectiveness.
• CFPP stands for "Cold Filter Plugging Point”.
• the viscosity ⁇ spec / c is determined in accordance with DIN 1342, DIN 51 562 and DIN 7745.
• the melt viscosity [MFI] is determined in accordance with DIN 53 735 or ASTM 1268-62T.
• the ethylene-vinyl acetate copolymers and terpolymers which are used in the examples below have a degree of branching between 3 and 15 CH3 groups per 100 CH2 groups.
• ethylene-vinyl acetate copolymers and optionally polyalkyl (meth) acrylates are dissolved in kerosene (boiling point 180-220 degrees C) in the mixing ratio given in the respective examples by stirring at 80 degrees C within 2 hours.
• the amount of kerosene is chosen so that 50% solutions result in all cases.
• EVA-A1 and 37.5 G EVA-B6 are dissolved in 750 g kerosene (180 - 210 ° C) by stirring at a temperature of 90 ° C.
• a mixture of 1,500 g of iso-C10 methacrylate and 22.5 g of tert-butyl peroctoate is then added to the solution presented under a nitrogen atmosphere within 2 hours by means of a metering pump at 90 ° C. After the feed has ended, a further 1.5 g of tert-butyl peroctoate are added.
• the total polymerization time is 16 hours.
• the polymer is composed of 47.5 parts EVA-A1, 2.5 parts EVA-B6 and 50 parts polyisodecyl methacrylate.
• the additional amounts of the additives each relate to the 50% solutions of Examples 1-8 or the 75% solutions of Example 10, which were heated before the addition.
• Samples of the additive DK are filled into graduated 20 ml measuring cylinders and cooled to a temperature 5 degrees C below the cloud point (CP). The sedimentation of the paraffin crystals is then observed as a function of time and stated in% sedimentation.
• the cloud point (CP) is determined in accordance with DIN 51 597.

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• 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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Lubricants (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1989
  • 1989-07-06 DE DE3922146A patent/DE3922146A1/de not_active Withdrawn
• 1990
  • 1990-06-27 EP EP90112229A patent/EP0406684B1/de not_active Expired - Lifetime
  • 1990-06-27 AT AT90112229T patent/ATE76093T1/de active
  • 1990-06-27 DE DE9090112229T patent/DE59000124D1/de not_active Expired - Lifetime
  • 1990-07-06 CA CA002020571A patent/CA2020571A1/en not_active Abandoned
  • 1990-07-06 JP JP2177630A patent/JPH0345693A/ja active Pending

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