EP0157268B1 - Injection improver for a fuel mixture - Google Patents
Injection improver for a fuel mixture Download PDFInfo
- Publication number
- EP0157268B1 EP0157268B1 EP85103095A EP85103095A EP0157268B1 EP 0157268 B1 EP0157268 B1 EP 0157268B1 EP 85103095 A EP85103095 A EP 85103095A EP 85103095 A EP85103095 A EP 85103095A EP 0157268 B1 EP0157268 B1 EP 0157268B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrocellulose
- parts
- ethylene oxide
- ignition
- fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000000446 fuel Substances 0.000 title claims description 39
- 238000002347 injection Methods 0.000 title description 4
- 239000007924 injection Substances 0.000 title description 4
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 34
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000003380 propellant Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- -1 cycloalkyl nitrates Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 229940042472 mineral oil Drugs 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- VOXVCYMHFQQEMC-UHFFFAOYSA-O triethylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH+](CC)CC VOXVCYMHFQQEMC-UHFFFAOYSA-O 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
- C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
-
- 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
- F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
- F02B2275/14—Direct injection into combustion chamber
Definitions
- the invention relates to ignition improvers for alcoholic fuels and alcoholic fuel mixtures which can be used for the operation of diesel engines.
- Methanol and ethanol cannot be used in place of the mineral hydrocarbons in conventional diesel engines because the cetane number of ethanol and methanol is only 8 and 3, respectively.
- diesel engines require a fuel with a cetane number of at least 45 (DIN 51 601; Winnacker-Küchler, Chemical Technology, Volume 3 / I. 326 (1971)).
- Ignition improvers are therefore required to increase the cetane number.
- Alkyl and cycloalkyl nitrates are known for fuels based on methanol and ethanol (DE-A-2 701 588, DE-A-20 39 609, Mineralogietechnik 80, 25 (4), 1 to 12), but their preparation is expensive and which can hydrolyze in the presence of water. This creates nitric acid, which destroys the motors through corrosion.
- Nitric acid salts of primary, secondary and tertiary amines, such as. B. mono-, di- and triethylammonium nitrate are known as ignition improvers for methanol and ethanol (DE-A-29 09 565), but they also have corrosive properties.
- ignition improvers for alcoholic fuels which contain nitric acid esters of mono- and / or polysaccharides, e.g. B. nitrocellulose.
- these ignition improvers are used in the fuel-carrying parts of the engines, however, films of nitrocellulose form on the walls, which can lead to solid, constipating residues. This disadvantage cannot be solved satisfactorily by adding further solvents.
- US-A-4,298,352 discloses the use of polyoxyalkylene compounds to increase the cetane number of fuels based on methanol.
- ignition improvers for alcoholic fuels for internal combustion engines which contain nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least three ethylene oxide units.
- the ignition improvers according to the invention do not leave any residues which lead to blockages. They are fully compatible with petroleum-based fuels.
- Nitrocellulose with a nitrogen content of 10 to 13% is preferred for the ignition improvers according to the invention.
- Nitrocelluloses which increase the viscosity of the alcoholic fuel as little as possible are particularly preferred. Therefore, according to the invention, nitrocelluloses with an intrinsic viscosity k of less than 1,000, preferably from 800 to 200, are used particularly advantageously.
- the intrinsic viscosity of nitrocellulose can be determined in a manner known per se (Fikentscher, Cellulosechemie 13, 58 (1932)).
- nitrocellulose for the ignition improvers is known per se (K. Fabel, nitrocellulose production and properties, Enke Verlag, Stuttgart (1950)). It can be produced, for example, by reacting it in a homogeneous and / or heterogeneous phase with nitric acid or its anhydride in the presence of water-drawing agents such as sulfuric acid, phosphoric acid, phosphorus pentoxide or acetic anhydride. The degree of nitration can be controlled as desired by the amount and concentration of the nitric acid or the dehydrating additives.
- Polyethers having at least three ethylene oxide units, preferably 4 to 100 ethylene oxide units, are used for the ignition improvers according to the invention. According to the invention, preference is given to polyethers which are prepared by reacting compounds which have at least one OH and / or NH group with ethylene oxide in a manner known per se. It is of course possible and possibly also technically expedient to use polyethers with different degrees of ethoxylation and different OH and NH compounds.
- the polyethers can also contain alkylene oxide units, preferably 0.1 to 0.5 propylene oxide units, based on an ethylene oxide unit.
- Alkyl here generally represents a straight-chain or branched hydrocarbon radical having 1 to 6 carbon atoms.
- the following alkyl radicals may be mentioned, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
- the compounds having at least one OH or NH group are substituted by further hydroxyamino groups, compounds having 1 to 5, preferably 1 or 2, hydroxyl and / or amino groups are preferred.
- Examples of compounds with an OH and / or NH group are water, mono- and polyols such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and nitrogen-containing compounds such as ammonia, ethanolamine, triethanolamine and dimethylethanolamine. Mixtures of these compounds can also be used as starter molecules for the addition of ethylene oxide. Water and lower mono- and polyols are particularly preferred as starters.
- the concentrates generally contain 15 to 60 parts by weight of nitrocellulose and 20 to 70 parts by weight of polyether.
- the ignition improvers according to the invention preferably contain 20 to 50 parts by weight of nitrocellulose and 30 to 60 parts by weight of polyether.
- the ignition improvers according to the invention can of course also contain other additives known per se.
- other, known ignition improvers as well as the addition of components that are suitable for diesel engine combustion, such as.
- the addition of detergents and starting aids is also possible.
- the fuels containing the ignition improvers according to the invention can be obtained directly from the individual components, i.e. H. Nitrocellulose, polyether and alcohol can be produced. However, it is preferred to prepare a concentrate consisting of these components, which is then to be diluted with alcohol to such an extent that the concentration of the ignition improver according to the invention ensures that an engine runs properly.
- the ignition improvers according to the invention can be used as an additive to alcoholic fuels.
- the present invention also relates to fuel mixtures which contain alcohol and an ignition improver which contains nitrocellulose with a nitrogen content of 9 to 14% and a polyether with at least three ethylene oxide units.
- the fuel mixtures according to the invention are suitable for the operation of diesel engines, in particular vehicle diesel engines and those which place similar demands on the fuel.
- alcohol is a lower aliphatic alcohol with 1 to 6 carbon atoms. Methanol and / or ethanol is particularly preferred here.
- the alcohols can optionally contain up to 10% by weight of water.
- ethanol can be used, which is obtained by fermentation and is produced as an azeotrope with 4.5% water.
- concentration of the nitrocellulose in the fuel mixtures according to the invention depends on the cetane number to be achieved. Concentrations of 2 to 12% by weight, preferably 4 to 8% by weight, are preferred for trouble-free operation in a conventional diesel engine.
- the concentration of the polyether in the fuel mixtures according to the invention depends on the concentration of the nitrocellulose, its k value and the desired consistency of the residue after the alcohol has evaporated.
- the ratio of nitrocellulose to polyether should be from 1: 0.2 to 1: 2.0. It is preferably 1: 0.5 to 1: 1.5, particularly preferably 1: 0.8 to 1: 1.2.
- polyethers with at least three ethylene oxide units are particularly advantageous since these products also serve as desensitizing agents for the nitrocellulose.
- the nitrocellulose can be mixed with the polyethers immediately after production, and it is therefore excluded that deflagrations or explosions occur during the transport of the nitrocellulose to be used as an ignition improver or after the alcohol component has evaporated.
- Another advantageous aspect of the use of ethylene oxide polyethers is their lubricating effect, which is particularly important since, in contrast to conventional diesel oil, lower alcohols have no self-lubricating effect.
- ethylene oxide polyethers with at least three ethylene oxide units can advantageously be used in ignition improvers, since low homologs of this class of compounds, which are likewise not volatile at room temperature, such as, for. B. ethylene glycol or diethylene glycol, not are suitable if they are used in a comparable way.
- the propylene oxide polyethers which are structurally closely related to the ethylene oxide polyethers, do not suppress the tendency to form films when used in terms of weight, even if they have three or more propylene oxide units.
- the plasticizers used for the nitrocelluloses in the paint sector such as. B. phthalate of butanol and 2-ethylhexanol also show poor effectiveness.
- the concentrate has a viscosity of 4,000 mPa - s (cp) at 25 ° C.
- a concentrate which must be diluted with three parts of ethanol to arrive at the mixture of embodiment A, is made from 32 parts of nitrocellulose, 50 parts of polyether and 18 parts of ethanol. At 25 ° C it has a viscosity of 60,000 mPa - s (cp).
- Example 1 The fuel mixture described in Example 1 is used in a diesel engine with direct injection, with 1.4 times the amount being injected in accordance with the lower calorific value of the mixture compared to conventional diesel fuel.
- the diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 6%.
- Example 2 The fuel mixture described in Example 2 is used in a prechamber diesel engine, double the amount of fuel being injected in accordance with the lower calorific value of the mixture.
- the diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 5%.
- a fuel mixture consisting of 6 parts of a nitrocellulose with a k value of 460, 6 parts of a homologue mixture of an ethylene oxide polyether started on water with an average of 8 ethylene oxide units and 88 parts of methanol are used in a direct-injection diesel engine, with twice the amount corresponding to the lower calorific value of the mixture Fuel compared to petroleum-based diesel fuel is used. Good runnability is obtained in all speed ranges, the ignition delay of the mixture according to the invention being identical to that of a conventional diesel fuel with a cetane number of 51.
- Equal parts of the fuel mixture described in Example 1 and of conventional diesel fuel are converted into an emulsion under the action of shear forces.
- the emulsion separates within 1 hour with the formation of the initial phases. Cloudiness or precipitation are not observed.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Fats And Perfumes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
Die Erfindung betrifft Zündverbesserer für alkoholische Treibstoffe und alkoholische Kraftstoffgemische, die für den Betrieb von Dieselmotoren verwendet werden können.The invention relates to ignition improvers for alcoholic fuels and alcoholic fuel mixtures which can be used for the operation of diesel engines.
Methanol und Ethanol können nicht anstelle der mineralischen Kohlenwasserstoffe in Dieselmotoren üblicher Bauart verwendet werden, da die Cetanzahl von Ethanol und Methanol nur 8 bzw. 3 beträgt. Dieselmotoren benötigen jedoch für den störungsfreien Betrieb einen Treibstoff mit einer Cetanzahl von mindestens 45 (DIN 51 601 ; Winnacker-Küchler, Chemische Technologie, Band 3/I. 326 (1971)).Methanol and ethanol cannot be used in place of the mineral hydrocarbons in conventional diesel engines because the cetane number of ethanol and methanol is only 8 and 3, respectively. For trouble-free operation, however, diesel engines require a fuel with a cetane number of at least 45 (DIN 51 601; Winnacker-Küchler, Chemical Technology, Volume 3 / I. 326 (1971)).
Zur Anhebung der Cetanzahl sind daher Zündverbesserer erforderlich. Für Treibstoffe auf Basis von Methanol und Ethanol sind Alkyl- und Cycloalkylnitrate bekannt (DE-A-2 701 588, DE-A-20 39 609, Mineralogie Technik 80, 25 (4), 1 bis 12), deren Herstellung jedoch aufwendig ist und die in Anwesenheit von Wasser hydrolysieren können. Hierbei entsteht Salpetersäure, welche die Motoren durch Korrosion zerstört. Auch Salpetersäuresalze von primären, sekundären und tertiären Aminen, wie z. B. Mono-, Di-und Triethylammonium-nitrat sind als Zündverbesserer für Methanol und Ethanol bekannt (DE-A-29 09 565), jedoch weisen auch sie korrosive Eigenschaften auf.Ignition improvers are therefore required to increase the cetane number. Alkyl and cycloalkyl nitrates are known for fuels based on methanol and ethanol (DE-A-2 701 588, DE-A-20 39 609, Mineralogie Technik 80, 25 (4), 1 to 12), but their preparation is expensive and which can hydrolyze in the presence of water. This creates nitric acid, which destroys the motors through corrosion. Nitric acid salts of primary, secondary and tertiary amines, such as. B. mono-, di- and triethylammonium nitrate are known as ignition improvers for methanol and ethanol (DE-A-29 09 565), but they also have corrosive properties.
Aus der EP-A 0 071 134 sind Zündverbesserer für alkoholische Treibstoffe bekannt, die Salpetersäureester von Mono- und/oder Polysacchariden, z. B. Nitrocellulose, enthalten. Bei der Anwendung dieser Zündverbesserer in den kraftstofführenden Teilen der Motoren bilden sich jedoch Filme aus Nitrocellulose an den Wandungen, die zu festen, verstopfend wirkenden Rückständen führen können. Dieser Nachteil läßt sich durch den Zusatz von weiteren Lösungsmitteln nicht befriedigend lösen.From EP-A 0 071 134 ignition improvers for alcoholic fuels are known which contain nitric acid esters of mono- and / or polysaccharides, e.g. B. nitrocellulose. When these ignition improvers are used in the fuel-carrying parts of the engines, however, films of nitrocellulose form on the walls, which can lead to solid, constipating residues. This disadvantage cannot be solved satisfactorily by adding further solvents.
Bei der Verwendung von Treibstoffen auf Alkoholbasis mit den in der EP-A 0 071 134 offenbarten Zündverbesserern treten außerdem Probleme auf, wenn sie mit konventionellen Treibstoffen auf Mineralölbasis in Kontakt kommen. Durch die schlechtere Löslichkeit dieser Zündverbesserer in Mineralöl bedingt, treten Ausfällungen des Zündverbesserers auf, die ebenfalls zu einer Verstopfung des Motors führen.Problems also arise when using alcohol-based fuels with the ignition improvers disclosed in EP-A 0 071 134 if they come into contact with conventional mineral-oil-based fuels. Due to the poorer solubility of these ignition improvers in mineral oil, malfunctions of the ignition improver occur, which likewise lead to a blockage of the engine.
Aus der US-A-4 298 352 ist die Verwendung von Polyoxyalkylenverbindungen zur Anhebung der Cetanzahl von Treibstoffen auf Basis von Methanol bekannt.US-A-4,298,352 discloses the use of polyoxyalkylene compounds to increase the cetane number of fuels based on methanol.
Für die Anwendung in der Praxis ist die Kompatibilität von Treibstoffen auf Mineralölbasis und Alkoholbasis jedoch besonders wichtig.However, the compatibility of petroleum-based and alcohol-based fuels is particularly important for practical use.
Es wurden erfindungsgemäß Zündverbesserer für alkoholische Treibstoffe für Verbrennungskraftmaschinen gefunden, die Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und Polyether mit mindestens drei Ethylenoxideinheiten enthalten.According to the invention, ignition improvers for alcoholic fuels for internal combustion engines were found which contain nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least three ethylene oxide units.
Die erfindungsgemäßen Zündverbesserer hinterlassen bei der Anwendung in den Motoren keine Rückstände, die zu Verstopfungen führen. Sie sind völlig kompatibel gegenüber Treibstoffen auf Mineralölbasis.When used in the engines, the ignition improvers according to the invention do not leave any residues which lead to blockages. They are fully compatible with petroleum-based fuels.
Für die erfindungsgemäßen Zündverbesserer wird Nitrocellulose mit einem Stickstoffgehalt von 10 bis 13 % bevorzugt.Nitrocellulose with a nitrogen content of 10 to 13% is preferred for the ignition improvers according to the invention.
Besonders bevorzugt sind Nitrocellulosen, welche die Viskosität des alkoholischen Treibstoffes in möglichst geringem Maße erhöhen. Es werden daher erfindungsgemäß Nitrocellulosen mit einer Eigenviskosität k von kleiner als 1 000, bevorzugt von 800 bis 200, besonders vorteilhaft eingesetzt. Die Eigenviskosität der Nitrocellulose kann in an sich bekannter Weise bestimmt werden (Fikentscher, Cellulosechemie 13, 58 (1932)).Nitrocelluloses which increase the viscosity of the alcoholic fuel as little as possible are particularly preferred. Therefore, according to the invention, nitrocelluloses with an intrinsic viscosity k of less than 1,000, preferably from 800 to 200, are used particularly advantageously. The intrinsic viscosity of nitrocellulose can be determined in a manner known per se (Fikentscher, Cellulosechemie 13, 58 (1932)).
Die Herstellung der Nitrocellulose für die erfindungsgemäßen Zündverbesserer ist an sich bekannt (K. Fabel, Nitrocellulose-Herstellung und Eigenschaften, Enke Verlag, Stuttgart (1950)). Sie kann beispielsweise hergestellt werden, indem sie in homogener und/oder heterogener Phase mit Salpetersäure oder dessen Anhydrid in Anwesenheit von wasserziehenden Mitteln wie Schwefelsäure, Phosphorsäure, Phosphorpentoxid oder Essigsäureanhydrid umgesetzt wird. Der Nitrierungsgrad kann durch die Menge und Konzentration der Salpetersäure bzw. der wasserentziehenden Zusätze beliebig gesteuert werden.The production of the nitrocellulose for the ignition improvers according to the invention is known per se (K. Fabel, nitrocellulose production and properties, Enke Verlag, Stuttgart (1950)). It can be produced, for example, by reacting it in a homogeneous and / or heterogeneous phase with nitric acid or its anhydride in the presence of water-drawing agents such as sulfuric acid, phosphoric acid, phosphorus pentoxide or acetic anhydride. The degree of nitration can be controlled as desired by the amount and concentration of the nitric acid or the dehydrating additives.
Für die erfindungsgemäßen Zündverbesserer werden Polyether mit mindestens drei Ethylenoxideinheiten, bevorzugt 4 bis 100 Ethylenoxideinheiten, eingesetzt. Erfindungsgemäß werden Polyether bevorzugt, die durch Umsetzung von Verbindungen, die mindestens eine OH- und/oder NH-Gruppe aufweisen, mit Ethylenoxid in an sich bekannter Weise hergestellt werden. Es ist selbstverständlich möglich und gegebenenfalls auch technisch zweckmäßig Polyether mit verschiedenen Ethoxylierungsgraden und verschiedenen OH- und NH-Verbindungen einzusetzen. Die Polyether können außer den erfindungsgemäßen Ethylenoxideinheiten auch weiter Alkylenoxideinheiten, bevorzugt 0,1 bis 0,5 Propylenoxideinheiten, bezogen auf eine Ethylenoxideinheit, enthalten.Polyethers having at least three ethylene oxide units, preferably 4 to 100 ethylene oxide units, are used for the ignition improvers according to the invention. According to the invention, preference is given to polyethers which are prepared by reacting compounds which have at least one OH and / or NH group with ethylene oxide in a manner known per se. It is of course possible and possibly also technically expedient to use polyethers with different degrees of ethoxylation and different OH and NH compounds. In addition to the ethylene oxide units according to the invention, the polyethers can also contain alkylene oxide units, preferably 0.1 to 0.5 propylene oxide units, based on an ethylene oxide unit.
Als Verbindungen, die eine OH-Gruppe aufweisen, seien bevorzugt Verbindungen der Formel
Als Verbindungen, die eine NH-Gruppe aufweisen, seien bevorzugt Verbindungen der Formel
Alkyl steht hierbei im allgemeinen für einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen. Beispielsweise seien die folgenden Alkylreste genannt : Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, Pentyl, Isopentyl, Hexyl und Isohexyl.Alkyl here generally represents a straight-chain or branched hydrocarbon radical having 1 to 6 carbon atoms. The following alkyl radicals may be mentioned, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
Für den Fall, daß die Verbindungen mit mindestens einer OH- oder NH-Gruppe durch weitere Hydroxyaminogruppen substituiert sind, werden Verbindungen mit 1 bis 5, bevorzugt 1 oder 2, Hydroxy und/oder Aminogruppen bevorzugt.In the event that the compounds having at least one OH or NH group are substituted by further hydroxyamino groups, compounds having 1 to 5, preferably 1 or 2, hydroxyl and / or amino groups are preferred.
Beispiele für Verbindungen mit einer OH- und/oder NH-Gruppe sind Wasser, Mono- und Polyole wie Methanol, Ethanol, Propanol, Butanol, Amylalkohol, Ethylenglykol, Propylenglykol, Glycerin, Trimethylolpropan, Pentaerythrit, und stickstoffhaltige Verbindungen wie Ammoniak, Ethanolamin, Triethanolamin und Dimethylethanolamin. Als Startermoleküle für die Ethylenoxidanlagerung sind auch Gemische dieser Verbindungen einsetzbar. Besonders bevorzugt als Starter sind Wasser und niedere Mono- und Polyole.Examples of compounds with an OH and / or NH group are water, mono- and polyols such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and nitrogen-containing compounds such as ammonia, ethanolamine, triethanolamine and dimethylethanolamine. Mixtures of these compounds can also be used as starter molecules for the addition of ethylene oxide. Water and lower mono- and polyols are particularly preferred as starters.
Die Konzentrate enthalten im allgemeinen 15 bis 60 Gew.-Teile an Nitrocellulose und 20 bis 70 Gew.-Teile an Polyether. Bevorzugt enthalten die erfindungsgemäßen Zündverbesserer 20 bis 50 Gew.-Teile an Nitrocellulose und 30 bis 60 Gew.-Teile an Polyether.The concentrates generally contain 15 to 60 parts by weight of nitrocellulose and 20 to 70 parts by weight of polyether. The ignition improvers according to the invention preferably contain 20 to 50 parts by weight of nitrocellulose and 30 to 60 parts by weight of polyether.
Selbstverständlich können die erfindungsgemäßen Zündverbesserer noch andere, an sich bekannte Zusätze enthalten. Insbesondere zu nennen ist hier die Mitverwendung von weiteren, an sich bekannten Zündverbesserern, sowie der Zusatz von Komponenten, die für eine dieselmotorische Verbrennung geeignet sind, wie z. B. Propylenoxidpolyether, Fettalkohole, Fettsäureester, Dieselöl und pflanzliche Öle wie Soja-, Rizinus- oder Tallöl. Der Zusatz von Detergentien und Starthilfen ist ebenfalls möglich.The ignition improvers according to the invention can of course also contain other additives known per se. In particular, the use of other, known ignition improvers, as well as the addition of components that are suitable for diesel engine combustion, such as. B. propylene oxide polyethers, fatty alcohols, fatty acid esters, diesel oil and vegetable oils such as soybean, castor or tall oil. The addition of detergents and starting aids is also possible.
Die die erfindungsgemäßen Zündverbesserer enthaltenden Treibstoffe können direkt aus den Einzelkomponenten, d. h. Nitrocellulose, Polyether und Alkohol hergestellt werden. Bevorzugt ist jedoch die Herstellung eines aus diesen Komponenten bestehenden Konzentrates, welches dann mit Alkohol soweit zu verdünnen ist, daß die Konzentration des erfindungsgemäßen Zündverbesserers die einwandfreie Lauffähigkeit eines Motors gewährleistet.The fuels containing the ignition improvers according to the invention can be obtained directly from the individual components, i.e. H. Nitrocellulose, polyether and alcohol can be produced. However, it is preferred to prepare a concentrate consisting of these components, which is then to be diluted with alcohol to such an extent that the concentration of the ignition improver according to the invention ensures that an engine runs properly.
Die erfindungsgemäßen Zündverbesserer können als Zusatz zu alkoholischen Kraftstoffen verwendet werden.The ignition improvers according to the invention can be used as an additive to alcoholic fuels.
Gegenstand der vorliegenden Erfindung sind auch Kraftstoffgemische, die Alkohol und einen Zündverbesserer, der Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und einen Polyether mit mindestens drei Ethylenoxideinheiten enthält, enthalten. Die erfindungsgemäßen Kraftstoffgemische sind geeignet für den Betrieb von Dieselmotoren, insbesondere Fahrzeugdieselmotoren und solchen, die ähnliche Anforderungen an den Kraftstoff stellen.The present invention also relates to fuel mixtures which contain alcohol and an ignition improver which contains nitrocellulose with a nitrogen content of 9 to 14% and a polyether with at least three ethylene oxide units. The fuel mixtures according to the invention are suitable for the operation of diesel engines, in particular vehicle diesel engines and those which place similar demands on the fuel.
Alkohol ist erfindungsgemäß ein niederer aliphatischer Alkohol mit 1 bis 6 Kohlenstoffatomen. Insbesondere bevorzugt ist hier Methanol und/oder Ethanol. Die Alkohole können gegebenenfalls bis zu 10 Gew.-% Wasser enthalten. So kann beispielsweise Ethanol verwendet werden, das durch Gärung gewonnen wird, und dabei als Azeotrop mit 4,5 % Wasser anfällt.According to the invention, alcohol is a lower aliphatic alcohol with 1 to 6 carbon atoms. Methanol and / or ethanol is particularly preferred here. The alcohols can optionally contain up to 10% by weight of water. For example, ethanol can be used, which is obtained by fermentation and is produced as an azeotrope with 4.5% water.
Die Konzentration der Nitrocellulose in den erfindungsgemäßen Treibstoffgemischen ist abhängig von der zu erreichenden Cetanzahl. Für einen störungsfreien Betrieb in einem konventionellen Dieselmotor sind Konzentrationen von 2 bis 12 Gew.-%, bevorzugt 4 bis 8 Gew.-% bevorzugt.The concentration of the nitrocellulose in the fuel mixtures according to the invention depends on the cetane number to be achieved. Concentrations of 2 to 12% by weight, preferably 4 to 8% by weight, are preferred for trouble-free operation in a conventional diesel engine.
Die Konzentration des Polyethers in den erfindungsgemäßen Kraftstoffgemischen richtet sich nach der Konzentration der Nitrocellulose, ihrem k-Wert und der gewünschten Konsistenz des Rückstandes nach Verflüchtigung des Alkohols. Bei den erfindungsgemäßen Kraftstoffgemischen soll das Verhältnis von Nitrocellulose zu Polyether von 1 : 0,2 bis 1 : 2,0 betragen. Vorzugsweise beträgt es 1 : 0,5 bis 1 : 1,5, besonders bevorzugt 1 : 0,8 bis 1 : 1,2.The concentration of the polyether in the fuel mixtures according to the invention depends on the concentration of the nitrocellulose, its k value and the desired consistency of the residue after the alcohol has evaporated. In the fuel mixtures according to the invention, the ratio of nitrocellulose to polyether should be from 1: 0.2 to 1: 2.0. It is preferably 1: 0.5 to 1: 1.5, particularly preferably 1: 0.8 to 1: 1.2.
Man setzt im allgemeinen 3 bis 20 Gew.-Teile, bevorzugt 6 bis 15 Gew.-Teile des erfindungsgemäßen Zündverbesserers bezogen auf den Alkohol ein.In general, 3 to 20 parts by weight, preferably 6 to 15 parts by weight, of the ignition improver according to the invention, based on the alcohol, are used.
Die Verwendung von Polyethern mit mindestens drei Ethylenoxideinheiten ist besonders vorteilhaft, da diese Produkte gleichzeitig auch als Phlegmatisierungsmittel für die Nitrocellulose dienen. So kann die Nitrocellulose sofort nach der Herstellung mit den Polyethern vermischt werden und es ist somit ausgeschlossen, daß es während des Transportes der als Zündverbesserer einzusetzenden Nitrocellulose oder nach Verdunsten der Alkoholkomponente zu Verpuffungen oder Explosionen kommt. Ein weiterer vorteilhafter Aspekt der Mitverwendung von Ethylenoxidpolyethern ist ihre Schmierwirkung, die besonders wichtig ist, da niedere Alkohole im Gegensatz zu konventionellem Dieselöl keine selbstschmierende Wirkung besitzen.The use of polyethers with at least three ethylene oxide units is particularly advantageous since these products also serve as desensitizing agents for the nitrocellulose. Thus, the nitrocellulose can be mixed with the polyethers immediately after production, and it is therefore excluded that deflagrations or explosions occur during the transport of the nitrocellulose to be used as an ignition improver or after the alcohol component has evaporated. Another advantageous aspect of the use of ethylene oxide polyethers is their lubricating effect, which is particularly important since, in contrast to conventional diesel oil, lower alcohols have no self-lubricating effect.
Es ist besonders überraschend, daß nur Ethylenoxidpolyether mit mindestens drei Ethylenoxideinheiten vorteilhaft in Zündverbesserern eingesetzt werden können, da niedere, ebenfalls bei Raumtemperatur nicht flüchtige Homologe dieser Verbindungsklasse, wie z. B. Ethylengkykol oder Diethylenglykol, nicht geeignet sind, wenn sie vergleichbar angewendet werden. Überraschend ist auch die Tatsache, daß die mit den Ethylenoxidpolyethern strukturell eng verwandten Propylenoxidpolyether die Filmbildungstendenz bei gewichtsmäßig äquivalentem Einsatz nicht unterdrücken, auch wenn sie drei oder mehr Propylenoxideinheiten aufweisen. Auch die für die Nitrocellulosen im Lackbereich verwendeten Weichmacher, wie z. B. Phthalsäureester von Butanol und 2-Ethylhexanol zeigel ebenfalls eine schlechte Wirksamkeit.It is particularly surprising that only ethylene oxide polyethers with at least three ethylene oxide units can advantageously be used in ignition improvers, since low homologs of this class of compounds, which are likewise not volatile at room temperature, such as, for. B. ethylene glycol or diethylene glycol, not are suitable if they are used in a comparable way. It is also surprising that the propylene oxide polyethers, which are structurally closely related to the ethylene oxide polyethers, do not suppress the tendency to form films when used in terms of weight, even if they have three or more propylene oxide units. The plasticizers used for the nitrocelluloses in the paint sector, such as. B. phthalate of butanol and 2-ethylhexanol also show poor effectiveness.
8 Teile einer handelsüblichen Nitrocellulose (Stickstoffgehalt zwischen 10,0 und 11,5, k-Wert = 400) und 12,5 Teile eines Homologengemisches eines auf Wasser gestarteten Ethylenoxidpolyethers mit 4 bis 13 Ethylenoxideinheiten werden mit 80 Teilen 96 %igem Ethanol 15 Min. bei Raumtemperatur gerührt. Man erhält eine klare farblose Lösung.8 parts of a commercially available nitrocellulose (nitrogen content between 10.0 and 11.5, k value = 400) and 12.5 parts of a homologue mixture of a water-started ethylene oxide polyether with 4 to 13 ethylene oxide units are mixed with 80 parts of 96% ethanol for 15 minutes. stirred at room temperature. A clear, colorless solution is obtained.
24 Teile der Nitrocellulose und 37,5 Teile des Polyethers aus Ausführungsform A werden mit 38 Teilen 96 %igem Ethanols bis zum Erhalt einer klaren, gelblichen Lösung gerührt. Das Konzentrat weist bei 25 °C eine Viskosität von 4 000 mPa - s (cp) auf. Um die in Ausführungsform A beschriebene Mischung zu erhalten, muß ein Teil des Konzentrats mit zwei Teilen Ethanol verdünnt werden. Ein Konzentrat, welches mit drei Teilen Ethanol verdünnt werden muß, um zu dem Gemisch der Ausführungsform A zu gelangen, wird hergestellt aus 32 Teilen Nitrocellulose, 50 Teilen Polyether und 18 Teilen Ethanol. Es weist bei 25 °C eine Viskosität von 60 000 mPa - s (cp) auf.24 parts of the nitrocellulose and 37.5 parts of the polyether from embodiment A are stirred with 38 parts of 96% ethanol until a clear, yellowish solution is obtained. The concentrate has a viscosity of 4,000 mPa - s (cp) at 25 ° C. To obtain the mixture described in embodiment A, one part of the concentrate must be diluted with two parts of ethanol. A concentrate, which must be diluted with three parts of ethanol to arrive at the mixture of embodiment A, is made from 32 parts of nitrocellulose, 50 parts of polyether and 18 parts of ethanol. At 25 ° C it has a viscosity of 60,000 mPa - s (cp).
8 Teile einer handelsüblichen Nitrocellulose (Stickstoffgehalt zwischen 10,0 und 11,5 %, k-Wert 450) werden mit 12 Teilen eines auf Trimethylolpropan gestarteten Ethylenoxidpolyethers eines Molekulargewichts von 700 und 80 Teilen Methanol 15 Minuten bei Raumtemperatur gerührt. Man erhält eine klare, farblose Lösung.8 parts of a commercially available nitrocellulose (nitrogen content between 10.0 and 11.5%, k value 450) are stirred for 15 minutes at room temperature with 12 parts of an ethylene oxide polyether started on trimethylolpropane with a molecular weight of 700 and 80 parts of methanol. A clear, colorless solution is obtained.
Eine alkoholische Lösung, bei der das Verhältnis von der in Beispiel 1 verwendeten Nitrocellulose zu eingesetztem Hilfsstoff 1 1,5 beträgt, wird auf einer Glasplatte verstrichen. Man läßt den Alkohol vollständig verdampfen und prüft den Rückstand in seiner Konsistenz.
Die Beispiele zeigen, daß nur bei Verwendung der erfindungsgemäß einzusetzenden Ethylenoxidpolyether mit mindestens drei Ethylenoxideinheiten die verbleibenden Rückstände den Charakter einer hochviskosen Flüssigkeit mit z. T. noch schmierender Wirkung aufweisen. Alle anderen Substanzen bewirken bei gewichtsmäßig äquivalentem Einsatz Rückstände, welche nach Verdunsten des Treibstoffs bei beweglichen Teilen, z. B. in der Einspritzpumpe, Störungen hervorrufen würden.The examples show that only when using the ethylene oxide polyether to be used according to the invention with at least three ethylene oxide units, the remaining residues have the character of a highly viscous liquid with e.g. T. still have a lubricating effect. All other substances cause residues with equivalent weight use, which after evaporation of the fuel in moving parts such. B. in the injection pump, would cause interference.
In einem Dieselmotor mit Direkteinspritzung wird die in Beispiel 1 beschriebene Treibstoffmischung eingesetzt, wobei entsprechend dem geringeren Heizwert der Mischung gegenüber konventionellen Dieseltreibstoff die 1,4-fache Menge eingespritzt wird. Man erhält eine gute Lauffähigkeit des Dieselmotors mit einem dem konventionellen Dieseltreibstoff identischen Zündverzug. Die Lauffähigkeit des Motors ist auch dann noch gegeben, wenn die Konzentration der Nitrocellulose auf 6 % herabgesetzt wird.The fuel mixture described in Example 1 is used in a diesel engine with direct injection, with 1.4 times the amount being injected in accordance with the lower calorific value of the mixture compared to conventional diesel fuel. The diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 6%.
In einem Vorkammerdieselmotor wird die in Beispiel 2 beschriebene Treibstoffmischung eingesetzt, wobei entsprechend des geringeren Heizwertes der Mischung die doppelte Menge Treibstoff eingespritzt wird. Man erhält eine gute Lauffähigkeit des Dieselmotors mit einem dem konventionellen Dieseltreibstoff identischen Zündverzug. Die Lauffähigkeit des Motors ist auch dann noch gegeben, wenn die Konzentration der Nitrocellulose auf 5 % herabgesetzt wird.The fuel mixture described in Example 2 is used in a prechamber diesel engine, double the amount of fuel being injected in accordance with the lower calorific value of the mixture. The diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 5%.
Eine Treibstoffmischung bestehend aus 6 Teilen einer Nitrocellulose eines k-Wertes von 460, 6 Teilen eines Homologengemisches eines auf Wasser gestarteten Ethylenoxidpolyethers mit durchschnittlich 8 Ethylenoxideinheiten und 88 Teilen Methanol werden in einem direkt einspritzenden Dieselmotor eingesetzt, wobei entsprechend dem geringerem Heizwert der Mischung die doppelte Menge Treibstoff im Vergleich zu Dieselkraftstoff auf Mineralölbasis eingesetzt wird. Man erhält in allen Drehzahlbereichen eine gute Lauffähigkeit, wobei der Zündverzug der erfindungsgemäßen Mischung mit dem eines konventionellen Dieseltreibstoffes einer Cetanzahl von 51 identisch ist.A fuel mixture consisting of 6 parts of a nitrocellulose with a k value of 460, 6 parts of a homologue mixture of an ethylene oxide polyether started on water with an average of 8 ethylene oxide units and 88 parts of methanol are used in a direct-injection diesel engine, with twice the amount corresponding to the lower calorific value of the mixture Fuel compared to petroleum-based diesel fuel is used. Good runnability is obtained in all speed ranges, the ignition delay of the mixture according to the invention being identical to that of a conventional diesel fuel with a cetane number of 51.
Gleiche Teile der in Beispiel 1 beschriebenen Treibstoffmischung und von konventionellem Dieseltreibstoff werden unter Einwirkung von Scherkräften in eine Emulsion umgewandelt. Die Emulsion trennt sich innerhalb von 1 Stunde unter Ausbildung der Ausgangsphasen. Trübungen oder Ausfällungen werden nicht beobachtet.Equal parts of the fuel mixture described in Example 1 and of conventional diesel fuel are converted into an emulsion under the action of shear forces. The emulsion separates within 1 hour with the formation of the initial phases. Cloudiness or precipitation are not observed.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85103095T ATE30737T1 (en) | 1984-03-31 | 1985-03-18 | IGNITION IMPROVER FOR FUEL MIXTURES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3412078 | 1984-03-31 | ||
| DE19843412078 DE3412078A1 (en) | 1984-03-31 | 1984-03-31 | IGNITION ENVIRONMENT FOR FUEL MIXTURES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0157268A2 EP0157268A2 (en) | 1985-10-09 |
| EP0157268A3 EP0157268A3 (en) | 1986-04-09 |
| EP0157268B1 true EP0157268B1 (en) | 1987-11-11 |
Family
ID=6232250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85103095A Expired EP0157268B1 (en) | 1984-03-31 | 1985-03-18 | Injection improver for a fuel mixture |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4659335A (en) |
| EP (1) | EP0157268B1 (en) |
| JP (1) | JPS60219296A (en) |
| AT (1) | ATE30737T1 (en) |
| AU (1) | AU567397B2 (en) |
| BR (1) | BR8501449A (en) |
| DE (2) | DE3412078A1 (en) |
| DK (1) | DK144785A (en) |
| NO (1) | NO851034L (en) |
| NZ (1) | NZ211618A (en) |
| ZA (1) | ZA852392B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3711985A1 (en) * | 1987-04-09 | 1988-10-20 | Union Rheinische Braunkohlen | USE OF POLYOLETHERS TO PREVENT OR REDUCE DEPOSITS IN MIXTURE PROCESSING SYSTEMS |
| US4800847A (en) * | 1987-06-05 | 1989-01-31 | Pritchard Huw O | Anaerobic operation of an internal combustion engine |
| US4992605A (en) * | 1988-02-16 | 1991-02-12 | Craig Wayne K | Production of hydrocarbons with a relatively high cetane rating |
| SE463028B (en) * | 1988-02-22 | 1990-10-01 | Berol Kemi Ab | ETHANOL BRAZLE AND ITS APPLICATION AS DIESEL BRAZEN |
| US6280487B1 (en) * | 1991-12-24 | 2001-08-28 | Jgs Research Company, Inc. | Process for preparing ignition promoter, and fuel containing an ignition promoter |
| US7261063B1 (en) | 2006-06-28 | 2007-08-28 | Holland John J | Apparatus and method for using pure dry biomass carbohydrates as fuels, fuel extenders, and fuel oxygenates |
| BRPI0803522A2 (en) * | 2008-09-17 | 2010-06-15 | Petroleo Brasileiro Sa | diesel cycle fuel compositions containing dianhydrohexitols and derivatives |
| US8586520B2 (en) | 2011-06-30 | 2013-11-19 | Exxonmobil Research And Engineering Company | Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers |
| US20130023455A1 (en) | 2011-06-30 | 2013-01-24 | Exxonmobil Research And Engineering Company | Lubricating Compositions Containing Polyetheramines |
| WO2015049184A1 (en) * | 2013-10-01 | 2015-04-09 | Akzo Nobel Chemicals International B.V. | A methanol-based diesel fuel and the use of an ignition improver |
| UA124226C2 (en) | 2015-01-30 | 2021-08-11 | Анхесер-Бюш Інбев С.А. | Pressurized beverage concentrates and appliances and methods for producing beverages therefrom |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2046101A (en) * | 1932-03-18 | 1936-06-30 | Sternau & Co Inc S | Solidified composition |
| US2001070A (en) * | 1932-04-29 | 1935-05-14 | Hercules Powder Co Ltd | Nitrocellulose gel and method of producing |
| CH174405A (en) * | 1933-01-19 | 1935-01-15 | Apostolou Antonio | A process for the preparation of spark ignitable products from solid fuels, and resulting product. |
| US1995911A (en) * | 1933-02-07 | 1935-03-26 | Us Ind Alcohol Co | Method of making artificial fuel |
| US2965678A (en) * | 1951-12-28 | 1960-12-20 | Gen Aniline & Film Corp | Polyoxyethylene ethers of branched chain alcohols |
| US3672851A (en) * | 1971-04-26 | 1972-06-27 | Joseph M Ihm | Gelled alcohol fuel containing nitrocellulose and boric acid |
| US4298352A (en) * | 1977-11-29 | 1981-11-03 | Berol Kemi Ab | Diesel fuel comprising methanol and a methanol-soluble polyoxyalkylene compound |
| DE2909565A1 (en) * | 1979-03-12 | 1980-09-25 | Basf Ag | Alcohol and glycol ether diesel fuels - contg. tri:ethyl-ammonium nitrate to increase cetane number |
| US4332594A (en) * | 1980-01-22 | 1982-06-01 | Chrysler Corporation | Fuels for internal combustion engines |
| DE3129271A1 (en) * | 1981-07-24 | 1983-02-10 | Bayer Ag, 5090 Leverkusen | IGNITION ENVIRONMENT FOR COMBUSTION ENGINES |
-
1984
- 1984-03-31 DE DE19843412078 patent/DE3412078A1/en not_active Withdrawn
-
1985
- 1985-03-13 AU AU39806/85A patent/AU567397B2/en not_active Ceased
- 1985-03-15 NO NO851034A patent/NO851034L/en unknown
- 1985-03-18 AT AT85103095T patent/ATE30737T1/en not_active IP Right Cessation
- 1985-03-18 EP EP85103095A patent/EP0157268B1/en not_active Expired
- 1985-03-18 DE DE8585103095T patent/DE3560951D1/en not_active Expired
- 1985-03-25 US US06/715,566 patent/US4659335A/en not_active Expired - Fee Related
- 1985-03-28 NZ NZ211618A patent/NZ211618A/en unknown
- 1985-03-28 JP JP60062207A patent/JPS60219296A/en active Pending
- 1985-03-29 DK DK144785A patent/DK144785A/en not_active Application Discontinuation
- 1985-03-29 BR BR8501449A patent/BR8501449A/en unknown
- 1985-03-29 ZA ZA852392A patent/ZA852392B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK144785A (en) | 1985-10-01 |
| DK144785D0 (en) | 1985-03-29 |
| NO851034L (en) | 1985-10-01 |
| ATE30737T1 (en) | 1987-11-15 |
| BR8501449A (en) | 1985-11-26 |
| JPS60219296A (en) | 1985-11-01 |
| EP0157268A2 (en) | 1985-10-09 |
| US4659335A (en) | 1987-04-21 |
| AU3980685A (en) | 1985-10-03 |
| AU567397B2 (en) | 1987-11-19 |
| NZ211618A (en) | 1987-09-30 |
| ZA852392B (en) | 1985-11-27 |
| DE3560951D1 (en) | 1987-12-17 |
| DE3412078A1 (en) | 1985-10-03 |
| EP0157268A3 (en) | 1986-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3149170C2 (en) | ||
| DE69415617T2 (en) | Diesel fuel | |
| EP0209758B1 (en) | Motor fuels and heating oils and use of an emulgator system in the preparation of these motor fuels and heating oils | |
| EP0289785B1 (en) | Process to prevent or reduce scales in mixture preparation devices of engines | |
| EP0012345B1 (en) | Fuel oils and their application | |
| EP0157268B1 (en) | Injection improver for a fuel mixture | |
| DE69730709T2 (en) | FUEL ADDITIVES | |
| DD147683A5 (en) | FUELS AND HEATING OIL, METHOD FOR THEIR PRODUCTION AND THEIR USE | |
| DE2027129A1 (en) | Fuel mixture | |
| DE69410801T2 (en) | FUEL BASED ON ETHANOL AND APPLICATION OF AN IGNITION ENHANCER | |
| DE3150988C2 (en) | ||
| EP0014992B1 (en) | Application of polyethers and acetals based on methanol and/or ethanol as fuels for diesel engines and fuels for diesel engines comprising these compounds | |
| DE69810746T2 (en) | OXYGEN PRODUCTS AS DIESEL FUEL | |
| DE3876336T2 (en) | LUBRICATING OIL COMPOSITIONS WITH MULTIFUNCTIONAL ADDITIONAL COMPONENTS. | |
| DE3852668T3 (en) | Fuel composition with an additive to reduce valve seat kickback. | |
| DE4308053A1 (en) | Liquid fuels | |
| DE1102477B (en) | Liquid petrol-based fuel for gasoline engines | |
| DE4333418C1 (en) | Fuel mixture | |
| DE3307091C2 (en) | ||
| DE60125672T2 (en) | Tetrahydrofurfuryl-derived, oxygen-containing compounds containing diesel fuel compositions | |
| EP0071134B1 (en) | Ignition improver for combustion engines | |
| DE2753027A1 (en) | USE OF A COMPOSITION BASED ON METHANOL AS DIESEL FUEL | |
| DE2062034A1 (en) | ||
| DE2102559A1 (en) | New imide compounds, processes for their production and their use as fuel additives | |
| DE3345516C2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19850318 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19870120 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| ITF | It: translation for a ep patent filed | ||
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| REF | Corresponds to: |
Ref document number: 30737 Country of ref document: AT Date of ref document: 19871115 Kind code of ref document: T |
|
| ET | Fr: translation filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REF | Corresponds to: |
Ref document number: 3560951 Country of ref document: DE Date of ref document: 19871217 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19890318 Ref country code: AT Effective date: 19890318 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19890319 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19890331 Ref country code: CH Effective date: 19890331 Ref country code: BE Effective date: 19890331 |
|
| BERE | Be: lapsed |
Owner name: BAYER A.G. Effective date: 19890331 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19891001 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19891130 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19891201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| EUG | Se: european patent has lapsed |
Ref document number: 85103095.7 Effective date: 19891016 |