EP2038380B1 - Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels - Google Patents
Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels Download PDFInfo
- Publication number
- EP2038380B1 EP2038380B1 EP07730085A EP07730085A EP2038380B1 EP 2038380 B1 EP2038380 B1 EP 2038380B1 EP 07730085 A EP07730085 A EP 07730085A EP 07730085 A EP07730085 A EP 07730085A EP 2038380 B1 EP2038380 B1 EP 2038380B1
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- EP
- European Patent Office
- Prior art keywords
- oil
- fuels
- weight
- acid
- mixture
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000000446 fuel Substances 0.000 title claims abstract description 68
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 43
- 150000001408 amides Chemical class 0.000 title claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 14
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 7
- 150000002830 nitrogen compounds Chemical class 0.000 title claims abstract description 7
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 9
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 8
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
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- -1 amide ammonia salt Chemical class 0.000 claims description 22
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- 150000001412 amines Chemical class 0.000 claims description 15
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- WBZPMFHFKXZDRZ-UHFFFAOYSA-N ethenyl 6,6-dimethylheptanoate Chemical compound CC(C)(C)CCCCC(=O)OC=C WBZPMFHFKXZDRZ-UHFFFAOYSA-N 0.000 description 1
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QUISWUAUMRRNFA-UHFFFAOYSA-N n-docosyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCCCCCC QUISWUAUMRRNFA-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ASLXNOZOXWPTNG-UHFFFAOYSA-N tricosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCN ASLXNOZOXWPTNG-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C10L1/22—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
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- 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
- 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
- C10L10/16—Pour-point depressants
-
- 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
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
-
- 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
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- 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
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
Definitions
- the present invention relates to the use of this mixture as an additive to fuels, especially in the function as a paraffin dispersant, such fuels themselves and fuel additive concentrates containing this mixture dissolved in a hydrocarbon solvent.
- the fuels mentioned have in particular a biodiesel component.
- Middle distillate fuels of fossil origin especially gas oils, diesel oils or light fuel oils derived from petroleum, have different levels of paraffins depending on the source of the crude oil.
- cloudy point or Cloud Point (“CP") precipitates solid paraffins.
- the platy n-paraffin crystals form a kind of "house of cards structure” and the middle distillate fuel stagnates, although its predominant part is still liquid.
- the precipitated n-paraffins in the temperature range between cloud point (cloud point) and pour point (pour point) the flowability of middle distillate fuels is significantly affected;
- the paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar disturbances occur with light fuel oils.
- ethylene-vinyl carboxylate copolymers have long been used as cold flow improvers or Middle Distillate Flow Improvers ("MDFI").
- MDFI Middle Distillate Flow Improvers
- a disadvantage of these additives is that the precipitated paraffin crystals tend due to their relative to the liquid part higher density tend to settle more and more at the bottom of the container during storage. As a result, a homogeneous low-paraffin phase forms in the upper container part and a two-phase paraffin-rich layer at the bottom. Since the deduction of the fuel usually takes place slightly above the container bottom both in the vehicle tanks and in storage or delivery tanks of the mineral oil dealer, there is the risk that the high concentration of solid paraffins leads to blockages of filters and metering devices. This danger is greater the further the storage temperature falls below the excretion temperature of the paraffins, since the amount of paraffin precipitated increases with decreasing temperature. In particular, levels of biodiesel also enhance this undesirable tendency of the middle distillate fuel to paraffin sedimentation.
- WO 00/23541 (1) is the use of a mixture of 5 to 95 wt .-% of at least one reaction product of a poly (C 2 - to C 20 carboxylic acid having at least one tertiary amino group) with secondary amines and 5 to 95 Wt .-% of at least one reaction product of maleic anhydride and a primary alkylamine as an additive for petroleum middle distillates, in particular as paraffin dispersant and lubricity additive described.
- the GB-A 1 410 788 discloses a fuel additive composition consisting of a fatty acid amide of aliphatic polyamines and an alkanolamine ester of a fatty or naphthenic acid in the weight ratio of 1: 8 to 8: 1.
- the GB-A 842 991 discloses a fuel additive composition consisting of a fatty acid amide of ethylene diamine with oleic acid and a diethylaminoethyl methacrylate based copolymer.
- the object was to provide products which ensure improved fluidity behavior of fuels, in particular those fuels which have a proportion of biofuel (biodiesel) which is based on fatty acid esters, at low temperature, by exhibiting such a dispersing action in that settling of excreted paraffins is delayed or prevented.
- biofuel biodiesel
- the object is achieved by the above-mentioned mixture of components (a) to (c), which is all the more surprising, since the components (a) and (b) alone respectively no or only a small, not sufficient flow improving Effect in a mixture of a conventional middle distillate of fossil origin and a biofuel oil which is based on fatty acid esters have.
- the component (c) is not necessarily necessary for achieving the intended flowability improvement, but usually significantly enhances this effect.
- the polar, oil-soluble nitrogen compounds of component (a) which are capable of sufficiently dispersing paraffin crystals precipitated in fuels in the cold can be both ionic and nonionic and preferably have at least one, especially at least 2, substituents of the general 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. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having up to 4 carboxyl groups or with a suitable derivative thereof.
- the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
- 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, in the chapter "Amines, aliphatic".
- suitable polar, oil-soluble nitrogen compounds are ring systems bearing at least two substituents of the formula -A'-NR 23 R 24 , wherein A 'represents a linear or branched aliphatic hydrocarbon group optionally substituted by one or more moieties selected is interrupted by O, S, NR 35 and CO, and R 23 and R 24 are a C 9 to C 40 hydrocarbon radical optionally substituted by one or more moieties selected from O, S, NR 35 and CO, interrupted and / or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 - to C 40 -alkyl optionally substituted by one or more moieties are selected from CO, NR 35 , O and S, interrupted, and / or by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COLOR 37 , CONR 37 R 38 , aryl or heterocyclyl, s is substitute
- the mixture according to the invention contains as component (a) at least one oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
- the component (a) underlying at least one tertiary amino group-containing poly (C 2 - to C 20 carboxylic acids) preferably contain at least 3 carboxyl groups, especially 3 to 12, especially 3 to 5 carboxyl groups.
- the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
- the carboxylic acid units are suitably linked to the polycarboxylic acids, for example via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
- the mixture according to the invention contains as component (a) at least one oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of general formula I or II containing at least one tertiary amino group in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 - to C 19 -alkylene group.
- oil-soluble reaction product of component (a), in particular that of the general formula I or II, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups are converted into amide groups.
- Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene.
- the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
- C 1 - to C 19 -alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene.
- the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
- the primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (a) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
- These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
- the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives.
- the two radicals R are the same.
- the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present.
- the oil-soluble reaction products of component (a) are completely in the form of the amide structures.
- components (a) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, Dipalmitinamine, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin.
- a particularly preferred component (a) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
- the polyamines on which the oil-soluble acid amides of component (b) are based can either be structurally clearly defined low molecular weight "oligo" amines or polymers having up to 1000, in particular up to 500, especially up to 100, nitrogen atoms in the macromolecule.
- oligo low molecular weight
- the latter are then usually polyalkyleneimines, for example polyethyleneimines, or polyvinylamines.
- the polyamines mentioned are reacted with C 8 - to C 30 -fatty acids, in particular C 16 - to C 20 -fatty acids, to give the oil-soluble acid amides.
- C 8 - to C 30 -fatty acids in particular C 16 - to C 20 -fatty acids
- reactive fatty acid derivatives such as the corresponding esters, halides or anhydrides, for the reaction.
- Suitable polyamines for the conversion to the acid amides of component (b) are, for example: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, polyethyleneimines of average degree of polymerization (corresponding to the number of nitrogen atoms) of e.g. , B. 10, 35, 50 or 100 and polyamines, which were obtained by reaction of oligoamines (with chain extension) with acrylonitrile and subsequent hydrogenation, for. N, N'-bis (3-aminopropyl) ethylenediamine.
- Suitable fatty acids for the conversion to the acid amides of component (b) are pure fatty acids and technically customary fatty acid mixtures which comprise, for example, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and / or linolenic acid.
- fatty acid mixtures for example tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.
- the mixture according to the invention contains as component (b) at least one oil-soluble acid amide of aliphatic polyamines having 2 to 6 nitrogen atoms and C 16 - to C 20 -fatty acids, all primary and secondary amino functions of the polyamines being converted into acid amide functions.
- a typical example of an oil-soluble acid amide of component (b) is the reaction product of 3 moles of oleic acid with 1 mole of diethylenetriamine.
- the oil-soluble reaction products of component (c) underlying ⁇ , ⁇ -dicarboxylic acids having 4 to 300, especially 4 to 75, especially 4 to 12 carbon atoms are usually succinic acid, maleic acid, fumaric acid or derivatives thereof, at the bridging ethylene or Ethenylene group may have shorter or longer chain hydrocarbyl substituents which contain or may carry heteroatoms and / or functional groups.
- succinic acid, maleic acid, fumaric acid or derivatives thereof at the bridging ethylene or Ethenylene group may have shorter or longer chain hydrocarbyl substituents which contain or may carry heteroatoms and / or functional groups.
- these are generally used in the form of the free dicarboxylic acid or its reactive derivatives.
- Carboxylic acid halides, carboxylic acid esters or, in particular, carboxylic acid anhydrides can be used here as reactive derivatives.
- the mixture according to the invention contains as component (c) at least one oil-soluble reaction product of maleic anhydride and primary alkylamines.
- the primary alkylamines underlying the oil-soluble reaction products of component (c) are usually medium-chain or long-chain alkyl monoamines preferably having 8 to 30, in particular 12 to 22 carbon atoms, and linear or branched, saturated or unsaturated alkyl chain, for example octyl, nonyl, iso-nonyl -, decyl, undecyl, tridecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylamine and mixtures of such amines.
- alkyl monoamines preferably having 8 to 30, in particular 12 to 22 carbon atoms, and linear or branched, saturated or unsaturated alkyl chain, for example octyl, nonyl, iso-nonyl -, decyl, undecyl, tridecyl, iso-tride
- reaction products of component (c) are usually - depending on the stoichiometry and reaction regime - as half or bisamides of maleic acid before; they may also contain minor amount of corresponding ammonium salts.
- the preparation of the oil-soluble reaction products of component (c) from maleic anhydride and primary alkylamines is described in document (1).
- a typical example of an oil-soluble reaction product of component (c) is the reaction product of 1 mol of maleic anhydride with 1 mol of iso-tridecylamine, which is present predominantly as a half-amide of maleic acid.
- the mixture according to the invention can be prepared by simple mixing, optionally in a suitable solvent, of components (a) and (b) or (a) to (c) without heat input.
- the mixture according to the invention is suitable as an additive to fuels, especially middle distillate fuels.
- Middle distillate fuels which are used in particular as gas oils, petroleum, diesel oils (diesel fuels) or light fuel oils, are often referred to as fuel oils.
- Such middle distillate fuels generally have boiling temperatures of 150 to 400 ° C.
- the mixture according to the invention can be injected directly into the fuels, i. undiluted, but preferably as 10 to 70 wt .-%, in particular as 30 to 65 wt .-%, especially as 45 to 60 wt .-% solution (concentrate) in a suitable solvent, usually a hydrocarbon solvent be added.
- a suitable solvent usually a hydrocarbon solvent be added.
- Common solvents in this context are aliphatic or aromatic hydrocarbons, for example xylenes or mixtures of high-boiling aromatics such as solvent naphtha. Even middle distillate fuels themselves can be used as solvents for such concentrates.
- the metering rate of the mixture in the fuels is generally 10 to 10,000 ppm by weight, in particular 50 to 5000 ppm by weight, especially 50 to 1000 ppm by weight, e.g. 150 to 400 ppm by weight, based in each case on the total amount of middle distillate fuel.
- the fuel component (A) is usually referred to as "biodiesel".
- the middle distillates of the fuel component (A) are preferably substantially alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
- Alkyl esters are usually lower alkyl esters, in particular C 1 - to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, such as ethanol, n-propanol, isoPropanol , n-butanol, iso-butanol, sec-butanol, tert-butanol, or especially methanol ("FAME").
- FAME methanol
- Examples of vegetable oils which are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil, and in particular sunflower oil, palm oil, soybean oil and rapeseed oil.
- Other examples include oils that can be extracted from wheat, jute, sesame and the shea nut; furthermore, arachis oil, jatropha oil and linseed oil are also usable. The recovery of these oils and their conversion to the alkyl esters are known in the art or may be derived therefrom.
- Vegetable fats are also useful in principle as a source of biodiesel, but play a minor role.
- animal fats and oils that are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are fish oil, beef tallow, Pig tallow and similar fats and oils derived from the slaughtering or recycling of farmed or wild animals.
- saturated or unsaturated fatty acids which usually have from 12 to 22 carbon atoms and may carry additional functional group such as hydroxyl groups, occur in the alkyl esters in particular lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid , Linoleic, linolenic, elaidic, erucic and ricinolic acids, especially in the form of mixtures of such fatty acids.
- Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biodiesel or biodiesel components are, for example, sunflower methyl ester, palm oil methyl ester ("PME”), soybean oil methyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”). ).
- fuel component (B) is to be understood to mean boiling middle distillate fuels in the range from 120 to 450 ° C.
- middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
- Middle distillate fuels are fuels obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C.
- low sulfur middle distillates are used, i. those containing less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur, especially less than 50 ppm of sulfur. In special cases they contain less than 10 ppm sulfur, these middle distillates are also called "sulfur-free".
- These are generally crude oil distillates, which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
- middle distillates which have 95% distillation points below 370 ° C., in particular below 350 ° C. and in special cases below 330 ° C.
- Low-sulfur and sulfur-free middle distillates can also be obtained from heavier petroleum fractions, which can no longer be distilled under atmospheric pressure.
- Hydrocarbon cracking, thermal cracking, catalytic cracking, coker processes and / or visbreaking may be mentioned as typical conversion processes for the preparation of middle distillates from heavy petroleum fractions. Depending on the procedure These middle distillates fall to low sulfur or sulfur-free or are subjected to a hydrogenating refining.
- the middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight.
- the content of normal paraffins is between 5% and 50% by weight, preferably between 10 and 35% by weight.
- middle distillates should also be understood here, which can be derived either indirectly from fossil sources such as crude oil or natural gas or else produced from biomass via gasification and subsequent hydrogenation.
- a typical example of a middle distillate fuel derived indirectly from fossil sources is GTL (gas-to-liquid) diesel fuel produced by Fischer-Tropsch synthesis.
- GTL gas-to-liquid diesel fuel produced by Fischer-Tropsch synthesis.
- a middle distillate is produced via the BTL (“bio-to-liquid”) process, which can be used either alone or in admixture with other middle distillates as fuel component (B).
- the middle distillates also include hydrocarbons obtained by hydrogenation of fats and fatty oils. They contain mostly n-paraffins.
- the said middle distillate fuels have in common that they are essentially hydrocarbon mixtures and are free from fatty acid esters.
- the mixture according to the invention is preferably used in the said fuels as a paraffin dispersant ("WASA").
- WASA paraffin dispersant
- the mixture according to the invention often unfolds its action as paraffin dispersant only particularly well together with the customary flow improvers.
- flow improvers are to be understood as meaning all additives which improve the cold properties of middle distillate fuels.
- MDFI actual cold flow improvers
- nucleators see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A16, page 719 ff.).
- the middle distillate fuels according to the invention contain in addition to the mixture according to the invention in the presence of cold flow improvers these in an amount of usually 1 to 2000 ppm by weight, preferably from 5 to 1000 ppm by weight, especially from 10 to 750 ppm by weight and especially from 50 to 500 ppm by weight, for example from 150 to 400 ppm by weight.
- the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters 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 ( ⁇ -olefins) and internally.
- ⁇ -olefins particularly preferably ⁇ -olefins having 3 to 6 carbon atoms, for example propene, 1-butene, 1-pentene and 1-hexene.
- Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 - to C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
- esters of (meth) acrylic acid with C 1 - to C 10 -alkanols in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Hexanol, heptanol, octanol, 2-ethylhe
- 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 preferred are those whose branch is in the ⁇ -position 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 esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred.
- a particularly preferred alkenyl carboxylic acid ester is vinyl acetate; typical copolymers of group (d) resulting therefrom are ethylene-vinyl acetate copolymers ("EVA”), which are widely used in diesel fuels.
- EVA ethylene-vinyl acetate copolymers
- the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.
- 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. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
- the ethylenically unsaturated monomer is in the copolymer of group (d) in an amount of preferably 1 to 50 mol .-%, in particular from 10 to 50 mol .-% and especially from 5 to 20 mol .-%, based on the total copolymer , copolymerized.
- the copolymer of group (d) preferably has a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.
- Preferred comb polymers are obtainable, 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 an alcohol having at least 10 carbon atoms.
- 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 suitable.
- Comb polymers may also be polyfumarates or polymaleinates.
- homopolymers and copolymers of vinyl ethers are suitable comb polymers.
- Preferred polyoxyalkylene compounds of the formula V 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 V 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.
- Suitable poly (meth) acrylic esters of group (h) 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 50,000 to 500,000.
- a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
- Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.
- the mixture according to the invention is an efficient one in its function as paraffin dispersant and versatile cold stabilization system for middle distillate fuels, especially those with a share of biodiesel.
- the use of the mixture according to the invention in particular in combination with flow improvers, can contribute to an improvement in the lubricating effect.
- the lubricating effect is determined, for example, in the so-called HFRR test according to ISO 12156.
- the mixture according to the invention can be added both middle distillate fuels, which are completely fossil origin, that is, derived from petroleum, as well as fuels containing a proportion of biodiesel in addition to the petroleum-based portion, to improve their properties.
- middle distillate fuels which are completely fossil origin, that is, derived from petroleum, as well as fuels containing a proportion of biodiesel in addition to the petroleum-based portion, to improve their properties.
- a significant improvement in the cold flow behavior of the middle distillate fuel i. a reduction in CP values and / or CFPP values, regardless of the origin or composition of the fuel observed.
- the precipitated paraffin crystals are effectively kept in suspension, so that there is no clogging of filters and lines by sedimented paraffin.
- the mixture according to the invention has a good broad action and thus effects that the precipitated paraffin crystals are very well dispersed in the most varied middle distillate fuels.
- the present invention also fuels, in particular those with a biodiesel content, which contain the mixture according to the invention.
- the fuels mentioned or the fuel additive concentrates mentioned contain further additives in customary amounts of flow improver (as described above), further paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, Detergents, cetane improvers, solvents or diluents, dyes or fragrances, or mixtures thereof.
- RME rapeseed oil methyl ester
- SME soybean oil methyl ester
- PME palm oil methyl ester
- FB1 and FB2 were selected for their CFPP performance in the diesel fuels used. It is very likely that other diesel fuels will require other MDFI. Thus, the blends of the invention are not limited to use in conjunction with FB1 and FB2.
- the additives K1 to K3 and FB1 or FB2 were each added separately to the diesel fuels. It is also possible to use the concentrates First mix K1, K2 and K3 with the MDFI FB1 or FB2 and then mix them together in the diesel fuels DK1 to DK7.
- the fuels DK1 to DK7 were admixed with the amounts of biodiesel additive specified in the table below, the concentrate K1, K2 or K3 and the flow improver FB1 or FB2, mixed with stirring at 40.degree. C. and then cooled to room temperature.
- the CP was determined according to ISO 3015 and the CFPP according to EN 116. Thereafter, the additized fuel samples were cooled in 500 ml glass cylinders in a cold bath from room temperature at a cooling rate of about 14 ° C per hour to -13 ° C and stored for 16 hours at this temperature.
- CP * (column 8) and CFPP * (column 11) indicate the values of the additized fuel samples before cooling.
- CP # (column 9) and CFPP # (column 12) indicate the corresponding values of the 20% by volume soil phase each separated after cooling.
- Column 10 is the absolute value of the difference from CP # to CP *.
- Column 13 indicates the vol .-% sediment of paraffin after storage in a cold bath at -13 ° C. If the specified value moves in the lower range (in the case of the examples listed below 40% by volume), the lower the value given here, the better the paraffin dispersing behavior. However, very high values in column 13 (in the case of the examples listed above 60% by volume) are also an indication of good paraffin dispersion behavior. Paraffin sedimentation is usually critical of about 10 to 30% by volume, since then most of the precipitated paraffin crystals are in the 20% by volume soil phase used to characterize the effectiveness of the additives as described.
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Abstract
Description
Die vorliegende Erfindung betrifft eine Mischung, enthaltend
- (a) 5 bis 95 Gew.-% mindestens einer von den Komponenten (b) und (c) verschiedenen polaren öllöslichen Stickstoffverbindung, welche in der Lage ist, in Kraftstoffen in der Kälte ausgefallene Paraffinkristalle ausreichend zu dispergieren, und ausgewählt ist unter Umsetzungsprodukten aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) mit primären oder sekundären Aminen,
- (b) 1 bis 50 Gew.-% mindestens eines öllöslichen Säureamids aus Polyaminen mit 2 bis 1000 Stickstoffatomen und C8- bis C30-Fettsäuren und
- (c) 0 bis 50 Gew.-% mindestens eines öllöslichen Umsetzungsproduktes aus α,β-Dicarbonsäuren mit 4 bis 300 Kohlenstoffatomen oder deren Derivaten und primären Alkylaminen,
- (a) 5 to 95% by weight of at least one polar oil-soluble nitrogen compound other than components (b) and (c) which is capable of sufficiently dispersing paraffin crystals precipitated in fuels in the cold and selected from reaction products at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines,
- (B) 1 to 50 wt .-% of at least one oil-soluble acid amide of polyamines having 2 to 1000 nitrogen atoms and C 8 - to C 30 fatty acids and
- (c) 0 to 50% by weight of at least one oil-soluble reaction product of α, β-dicarboxylic acids having 4 to 300 carbon atoms or derivatives thereof and primary alkylamines,
Weiterhin betrifft die vorliegende Erfindung die Verwendung dieser Mischung als Zusatz zu Kraftstoffen, insbesondere in der Funktion als Paraffindispergator, derartige Kraftstoffe selbst sowie Kraftstoffadditiv-Konzentrate, die diese Mischung gelöst in einem Kohlenwasserstoff-Lösungsmittel enthalten. Die genannten Kraftstoffe weisen insbesondere einen Biodiesel-Anteil auf.Furthermore, the present invention relates to the use of this mixture as an additive to fuels, especially in the function as a paraffin dispersant, such fuels themselves and fuel additive concentrates containing this mixture dissolved in a hydrocarbon solvent. The fuels mentioned have in particular a biodiesel component.
Mitteldestillat-Kraftstoffe aus fossilem Ursprung, insbesondere Gasöle, Dieselöle oder leichte Heizöle, die aus Erdöl gewonnen werden, haben je nach Herkunft des Rohöls unterschiedliche Gehalte an Paraffinen. Bei tiefen Temperaturen kommt es am Trübungspunkt oder Cloud Point ("CP") zur Ausscheidung fester Paraffine. Bei weiterer Abkühlung bilden die plättchenförmigen n-Paraffinkristalle eine Art von "Kartenhausstruktur" und der Mitteldestillat-Kraftstoff stockt, obwohl sein überwiegender Teil noch flüssig ist. Durch die ausgefallenen n-Paraffine im Temperaturbereich zwischen Trübungspunkt (Cloud Point) und Stockpunkt (Pour Point) wird die Fließfähigkeit der Mitteldestillat-Kraftstoffe erheblich beeinträchtigt; die Paraffine verstopfen Filter und verursachen eine ungleichmäßige oder völlig unterbrochene Kraftstoffzufuhr zu den Verbrennungsaggregaten. Ähnliche Störungen treten bei leichten Heizölen auf.Middle distillate fuels of fossil origin, especially gas oils, diesel oils or light fuel oils derived from petroleum, have different levels of paraffins depending on the source of the crude oil. At low temperatures cloudy point or Cloud Point ("CP") precipitates solid paraffins. Upon further cooling, the platy n-paraffin crystals form a kind of "house of cards structure" and the middle distillate fuel stagnates, although its predominant part is still liquid. The precipitated n-paraffins in the temperature range between cloud point (cloud point) and pour point (pour point), the flowability of middle distillate fuels is significantly affected; The paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar disturbances occur with light fuel oils.
Es ist seit langem bekannt, dass durch geeignete Zusätze das Kristallwachstum der n-Paraffine in Mitteldestillat-Kraftstoffen modifiziert werden kann. Gut wirksame Additive verhindern, dass Mitteldestillat-Kraftstoffe bei Temperaturen wenige Grade Celsius unterhalb der Temperatur, bei welcher die ersten Paraffinkristalle auskristallisieren, bereits fest werden. Statt dessen werden feine, gut kristallisierende, separate Paraffinkristalle gebildet, welche Filter in Kraftfahrzeugen und Heizungsanlagen passieren oder zumindest einen für den flüssigen Teil der Mitteldestillate durchlässigen Filterkuchen bilden, so dass ein störungsfreier Betrieb sichergestellt ist. Die Wirksamkeit der Fließverbesserer wird nach der europäischen Norm EN 116 indirekt durch Messung des Cold Filter Plugging Point ("CFPP") ausgedrückt.It has long been known that by appropriate additions, the crystal growth of n-paraffins in middle distillate fuels can be modified. Good effective additives prevent middle distillate fuels from already solidifying at temperatures a few degrees Celsius below the temperature at which the first paraffin crystals crystallize out. Instead, fine, well crystallizing, separate paraffin crystals are formed, which pass filters in motor vehicles and heating systems or at least form a permeable for the liquid part of the middle distillates filter cake, so that trouble-free operation is ensured. The effectiveness of the flow improvers is expressed indirectly according to the European standard EN 116 by measuring the Cold Filter Plugging Point ("CFPP").
Als Kaltfließverbesserer oder Middle Distillate Flow Improvers ("MDFI") werden seit langem beispielsweise Ethylen-Vinylcarboxylat-Copolymere eingesetzt. Ein Nachteil dieser Additive liegt darin, dass die ausgefallenen Paraffinkristalle aufgrund ihrer gegenüber dem flüssigen Teil höheren Dichte dazu neigen, sich beim Lagern mehr und mehr am Boden des Behälters abzusetzen. Dadurch bildet sich im oberen Behälterteil eine homogene paraffinarme Phase und am Boden eine zweiphasige paraffinreiche Schicht. Da sowohl in den Fahrzeugtanks als auch in Lager- oder Liefertanks der Mineralölhändler der Abzug des Kraftstoffes meist wenig oberhalb des Behälterbodens erfolgt, besteht die Gefahr, dass die hohe Konzentration an festen Paraffinen zu Verstopfungen von Filtern und Dosiereinrichtungen führt. Diese Gefahr wird um so größer, je weiter die Lagertemperatur die Ausscheidungstemperatur der Paraffine unterschreitet, da die ausgeschiedene Paraffinmenge mit sinkender Temperatur zunimmt. Insbesondere verstärken auch Anteile an Biodiesel diese unerwünschte Neigung des Mitteldestillat-Kraftstoffes zur Paraffinsedimentation.For example, ethylene-vinyl carboxylate copolymers have long been used as cold flow improvers or Middle Distillate Flow Improvers ("MDFI"). A disadvantage of these additives is that the precipitated paraffin crystals tend due to their relative to the liquid part higher density tend to settle more and more at the bottom of the container during storage. As a result, a homogeneous low-paraffin phase forms in the upper container part and a two-phase paraffin-rich layer at the bottom. Since the deduction of the fuel usually takes place slightly above the container bottom both in the vehicle tanks and in storage or delivery tanks of the mineral oil dealer, there is the risk that the high concentration of solid paraffins leads to blockages of filters and metering devices. This danger is greater the further the storage temperature falls below the excretion temperature of the paraffins, since the amount of paraffin precipitated increases with decreasing temperature. In particular, levels of biodiesel also enhance this undesirable tendency of the middle distillate fuel to paraffin sedimentation.
Durch den zusätzlichen Einsatz von Paraffindispergatoren oder Wax Anti-Settling Additiven ("WASA") können diese Probleme verringert werden.The additional use of paraffin dispersants or wax anti-settling additives ("WASA") can reduce these problems.
Im Zuge abnehmender Welterdölreserven und der Diskussion um die die Umwelt beeinträchtigenden Konsequenzen des Verbrauchs fossiler und mineralischer Brennstoffe steigt das Interesse an alternativen, auf nachwachsenden Rohstoffen basierenden Energiequellen. Dazu gehören insbesondere native Öle und Fette pflanzlichen oder tierischen Ursprungs. Dies sind insbesondere Triglyceride von Fettsäuren mit 10 bis 24 Kohlenstoffatomen, die zu Niedrigalkylestern wie Methylestern umgesetzt werden. Diese Ester werden allgemein auch als "FAME" (Fatty Acid Methyl Ester) bezeichnet.With decreasing world oil reserves and discussions about the environmental impact of fossil and mineral fuel consumption, there is a growing interest in alternative energy sources based on renewable raw materials. These include, in particular, natural oils and fats of plant or animal origin. These are in particular triglycerides of fatty acids having 10 to 24 carbon atoms which are converted to lower alkyl esters such as methyl esters. These esters are also commonly referred to as "FAME" (Fatty Acid Methyl Ester).
Mischungen dieser FAME mit Mitteldestillaten besitzen ein schlechteres Kälteverhalten als diese Mitteldestillate alleine. Insbesondere erhöht die Zugabe der FAME die Tendenz zur Bildung von Paraffinsedimenten.Mixtures of these FAME with middle distillates have a worse cold behavior than these middle distillates alone. In particular, the addition of FAME increases the tendency to form paraffin sediments.
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Es bestand die Aufgabe, Produkte zur Verfügung zu stellen, welche ein verbessertes Fließfähigkeitsverhalten von Kraftstoffen, insbesondere bei solchen Kraftstoffen, die einen Anteil an Biobrennstofföl (Biodiesel), welches auf Fettsäureestern basiert, aufweisen, bei tiefer Temperatur gewährleisten, indem sie eine solche Dispergierwirkung zeigen, dass ein Absetzen ausgeschiedener Paraffine verzögert oder verhindert wird.The object was to provide products which ensure improved fluidity behavior of fuels, in particular those fuels which have a proportion of biofuel (biodiesel) which is based on fatty acid esters, at low temperature, by exhibiting such a dispersing action in that settling of excreted paraffins is delayed or prevented.
Die Aufgabe wird erfindungsgemäß durch die eingangs genannte Mischung aus den Komponenten (a) bis (c) gelöst, was um so erstaunlicher ist, da die Komponenten (a) und (b) für sich alleine jeweils keine oder nur eine geringe, nicht ausreichende fließverbessernde Wirkung in einer Mischung aus einem üblichen Mitteldestillat fossilen Ursprungs und einem Biobrennstofföl, welches auf Fettsäureestern basiert, aufweisen. Die Komponente (c) ist nicht unbedingt zur Erzielung der beabsichtigen Fließfähigkeitsverbesserung notwendig, verstärkt diese Wirkung jedoch meist noch erheblich.The object is achieved by the above-mentioned mixture of components (a) to (c), which is all the more surprising, since the components (a) and (b) alone respectively no or only a small, not sufficient flow improving Effect in a mixture of a conventional middle distillate of fossil origin and a biofuel oil which is based on fatty acid esters have. The component (c) is not necessarily necessary for achieving the intended flowability improvement, but usually significantly enhances this effect.
Die polaren, öllöslichen Stickstoffverbindungen der Komponente (a), welche in der Lage sind, in Kraftstoffen in der Kälte ausgefallene Paraffinkristalle ausreichend zu dispergieren, können sowohl ionischer als auch nicht ionischer Natur sein und besitzen vorzugsweise wenigstens einen, insbesondere wenigstens 2 Substituenten der allgemeinen Formel >NR22, worin R22 für einen C8- bis C40-Kohlenwasserstoffrest steht. Die Stickstoffsubstituenten können auch quaternisiert, das heißt in kationischer Form, vorliegen. Beispiele für solche Stickstoffverbindungen sind Ammoniumsalze und/oder Amide, die durch die Umsetzung wenigstens eines mit wenigstens einem Kohlenwasserstoffrest substituierten Amins mit einer Carbonsäure mit bis zu 4 Carboxylgruppen bzw. mit einem geeignetem Derivat davon erhältlich sind. Vorzugsweise enthalten die Amine wenigstens einen linearen C8- bis C40-Alkylrest. Geeignete primäre Amine sind beispielsweise Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tetradecylamin und die höheren linearen Homologen. Geeignete sekundäre Amine sind beispielsweise Dioctadecylamin und Methylbehenylamin. Geeignet sind auch Amingemische, insbesondere großtechnisch zugängliche Amingemische wie Fettamine oder hydrierte Tallamine, wie sie beispielsweise in Ullmanns Encyclopedia of Industrial Chemistry, 6. Auflage, im Kapitel "Amines, aliphatic" beschrieben werden.The polar, oil-soluble nitrogen compounds of component (a) which are capable of sufficiently dispersing paraffin crystals precipitated in fuels in the cold can be both ionic and nonionic and preferably have at least one, especially at least 2, substituents of the general 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. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having up to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C 8 - to C 40 -alkyl radical. Examples of suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable are 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, in the chapter "Amines, aliphatic".
Weitere Beispiele für geeignete polare, öllösliche Stickstoffverbindungen sind Ringsysteme, die wenigstens zwei Substituenten der Formel -A'-NR23R24 tragen, worin A' für eine lineare oder verzweigte aliphatische Kohlenwasserstoffgruppe steht, die gegebenenfalls durch eine oder mehrere Gruppierungen, die ausgewählt sind unter O, S, NR35 und CO, unterbrochen ist, und R23 und R24 für einen C9- bis C40-Kohlenwasserstoffrest stehen, der gegebenenfalls durch eine oder mehrere Gruppierungen, die ausgewählt sind unter O, S, NR35 und CO, unterbrochen und/oder durch einen oder mehrere Substituenten, die ausgewählt sind unter OH, SH und NR35R36, substituiert ist, wobei R35 für C1- bis C40-Alkyl, das gegebenenfalls durch eine oder mehrere Gruppierungen, die ausgewählt sind unter CO, NR35, O und S, unterbrochen, und/oder durch einen oder mehrere Reste, die ausgewählt sind unter NR37R38, OR37, SR37, COR37, COLOR37, CONR37R38, Aryl oder Heterocyclyl, substituiert ist, wobei R37 und R38 jeweils unabhängig voneinander ausgewählt sind unter H oder C1- bis C4-Alkyl und wobei R36 für H oder R35 steht.Further examples of suitable polar, oil-soluble nitrogen compounds are ring systems bearing at least two substituents of the formula -A'-NR 23 R 24 , wherein A 'represents a linear or branched aliphatic hydrocarbon group optionally substituted by one or more moieties selected is interrupted by O, S, NR 35 and CO, and R 23 and R 24 are a C 9 to C 40 hydrocarbon radical optionally substituted by one or more moieties selected from O, S, NR 35 and CO, interrupted and / or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 - to C 40 -alkyl optionally substituted by one or more moieties are selected from CO, NR 35 , O and S, interrupted, and / or by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COLOR 37 , CONR 37 R 38 , aryl or heterocyclyl, s is substituted, wherein R 37 and R 38 are each independently selected from H or C 1 - to C 4 alkyl and wherein R 36 is H or R 35 .
Die erfindungsgemäße Mischung enthält als Komponente (a) mindestens ein öllösliches Umsetzungsprodukt aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) mit primären oder sekundären Aminen.The mixture according to the invention contains as component (a) at least one oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
Die der Komponente (a) zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) enthalten vorzugsweise mindestens 3 Carboxylgruppen, insbesondere 3 bis 12, vor allem 3 bis 5 Carboxylgruppen. Die Carbonsäure-Einheiten in den Polycarbonsäuren weisen vorzugsweise 2 bis 10 Kohlenstoffatome auf, insbesondere sind es Essigsäure-Einheiten. Die Carbonsäure-Einheiten sind in geeigneter Weise zu den Polycarbonsäuren verknüpft, beispielsweise über ein oder mehrere Kohlenstoff- und/oder Stickstoffatome. Vorzugsweise sind sie an tertiäre Stickstoffatome angebunden, die im Falle mehrerer Stickstoffatome über Kohlenwasserstoffketten verbunden sind.The component (a) underlying at least one tertiary amino group-containing poly (C 2 - to C 20 carboxylic acids) preferably contain at least 3 carboxyl groups, especially 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, for example via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
In einer bevorzugten Ausführungsform enthält die erfindungsgemäße Mischung als Komponente (a) mindestens ein öllösliches Umsetzungsprodukt auf Basis von mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) der allgemeinen Formel I oder II
Weiterhin ist das öllösliche Umsetzungsprodukt der Komponente (a), insbesondere das der allgemeinen Formel I oder II, ein Amid, ein Amidammoniumsalz oder ein Ammoniumsalz, in dem keine, eine oder mehrere Carbonsäuregruppen in Amidgruppen übergeführt sind.Furthermore, the oil-soluble reaction product of component (a), in particular that of the general formula I or II, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups are converted into amide groups.
Geradkettige oder verzweigte C2- bis C6-Alkylengruppen der Variablen A sind beispielsweise 1,1-Ethylen, 1,2-Propylen, 1,3-Propylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2-Methyl-1,3-propylen, 1,5-Pentylen, 2-Methyl-1,4-butylen, 2,2-Dimethyl-1,3-propylen, 1,6-Hexylen (Hexamethylen) und insbesondere 1,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome.Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
C1- bis C19-Alkylengruppen der Variablen B sind beispielsweise 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbesondere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome.C 1 - to C 19 -alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene. Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (a) sind üblicherweise Monoamine, insbesondere aliphatische Monoamine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen.The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (a) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
In einer bevorzugten Ausführungsform sind diese den Öllöslichen Umsetzungsprodukten der Komponente (a) zugrundeliegenden Amine sekundären Amine und weisen die allgemeine Formel HNR2 auf, in der die beiden Variablen R unabhängig voneinander jeweils geradkettige oder verzweigte C10- bis C30-Alkylreste, insbesondere C14- bis C24-Alkylreste bedeuten. Diese längerkettigen Alkylreste sind vorzugsweise geradkettig oder nur in geringem Grade verzweigt. In der Regel leiten sich die genannten sekundären Amine hinsichtlich ihrer längerkettigen Alkylreste von natürlich vorkommenden Fettsäure bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R gleich.In a preferred embodiment, these are the amines secondary amines underlying the oil-soluble reaction products of component (a) and have the general formula HNR 2 , in which the two variables R independently of one another in each case straight-chain or branched C 10 - to C 30 -alkyl radicals, especially C 14 - to mean C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives. Preferably, the two radicals R are the same.
Die genannten sekundären Amine können mittels Amidstrukturen oder in Form der Ammoniumsalze an die Polycarbonsäuren gebunden sein, auch kann nur ein Teil als Amidstrukturen und ein anderer Teil als Ammoniumsalze vorliegen. Vorzugsweise liegen nur wenige oder keine freien Säuregruppen vor. In einer bevorzugten Ausführungsform liegen die öllöslichen Umsetzungsprodukte der Komponente (a) vollständig in Form der Amidstrukturen vor.The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. In a preferred embodiment, the oil-soluble reaction products of component (a) are completely in the form of the amide structures.
Typische Beispiele für Komponenten (a) sind Umsetzungsprodukte der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure mit jeweils 0,5 bis 1,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1,2 Mol pro Carboxylgruppe, Dioleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditalgfettamin. Eine besonders bevorzugte Komponente (a) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditalgfettamin.Typical examples of components (a) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, Dipalmitinamine, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin. A particularly preferred component (a) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
Die den öllöslichen Säureamiden der Komponente (b) zugrundeliegenden Polyamine können entweder strukturell eindeutig definierte niedermolekulare "Oligo"amine oder Polymere mit bis zu 1000, insbesondere bis zu 500, vor allem bis zu 100 Stickstoffatomen im Makromolekül sein. Bei letzteren handelt es sich dann üblicherweise um Polyalkylenimine, beispielsweise Polyethylenimine, oder Polyvinylamine.The polyamines on which the oil-soluble acid amides of component (b) are based can either be structurally clearly defined low molecular weight "oligo" amines or polymers having up to 1000, in particular up to 500, especially up to 100, nitrogen atoms in the macromolecule. The latter are then usually polyalkyleneimines, for example polyethyleneimines, or polyvinylamines.
Die genannten Polyamine werden mit C8- bis C30-Fettsäuren, insbesondere C16- bis C20-Fettsäuren, zu den öllöslichen Säureamiden umgesetzt. Anstelle der freien Fettsäuren können zur Umsetzung prinzipiell auch reaktive Fettsäurederivate wie die entsprechenden Ester, Halogenide oder Anhydride verwendet werden.The polyamines mentioned are reacted with C 8 - to C 30 -fatty acids, in particular C 16 - to C 20 -fatty acids, to give the oil-soluble acid amides. In principle, instead of the free fatty acids, it is also possible to use reactive fatty acid derivatives, such as the corresponding esters, halides or anhydrides, for the reaction.
Die Umsetzung der Polyamine mit den Fettsäure zu den öllöslichen Säureamiden der Komponente (b) erfolgt vollständig oder partiell. Im letzteren Fall liegen meist untergeordnete Anteile des Produktes üblicherweise in Form von entsprechenden Ammoniumsalzen vor. Die Vollständigkeit der Umsetzung zu den Säureamiden lässt sich in der Regel jedoch durch die Umsetzungsparameter steuern. Die Herstellung der Säureamide der Komponente (b) ist in Dokument (2) beschrieben.The reaction of the polyamines with the fatty acid to the oil-soluble acid amides of component (b) takes place completely or partially. In the latter case, subordinate fractions of the product are usually present in the form of corresponding ammonium salts. The completeness of the conversion to the acid amides can be found in the However, control the rule by the conversion parameters. The preparation of the acid amides of component (b) is described in document (2).
Als für die Umsetzung zu den Säureamiden der Komponente (b) geeignete Polyamine sind beispielsweise zu nennen: Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin, Dipropylentriamin, Tripropylentetramin, Tetrapropylenpentamin, Pentapropylenhexamin, Polyethylenimine eines mittleren Polymerisationsgrades (entsprechend der Anzahl der Stickstoffatome) von z. B. 10, 35, 50 oder 100 sowie Polyamine, die durch Umsetzung von Oligoaminen (unter Kettenverlängerung) mit Acrylnitril und anschließende Hydrierung gewonnen wurden, z. B. N,N'-Bis-(3-aminopropyl)-ethylenediamin.Suitable polyamines for the conversion to the acid amides of component (b) are, for example: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, polyethyleneimines of average degree of polymerization (corresponding to the number of nitrogen atoms) of e.g. , B. 10, 35, 50 or 100 and polyamines, which were obtained by reaction of oligoamines (with chain extension) with acrylonitrile and subsequent hydrogenation, for. N, N'-bis (3-aminopropyl) ethylenediamine.
Als für die Umsetzung zu den Säureamiden der Komponente (b) geeignete Fettsäuren kommen reine Fettsäuren sowie technisch übliche Fettsäuregemische in Betracht, die beispielsweise Stearinsäure, Palmitinsäure, Laurinsäure, Ölsäure, Linolsäure und/oder Linolensäure enthalten. Von besonderem Interesse sind hierbei natürlich vorkommende Fettsäuregemische, beispielsweise Talgfettsäure, Kokosölfettsäure, Tranfettsäure, Kokospalmkernölfettsäure, Sojaölfettsäure, Rübölfettsäure, Erdnussölfettsäure oder Palmölfettsäure, welche als Hauptkomponenten Ölsäure und Palmitinsäure enthalten.Suitable fatty acids for the conversion to the acid amides of component (b) are pure fatty acids and technically customary fatty acid mixtures which comprise, for example, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and / or linolenic acid. Of particular interest here are naturally occurring fatty acid mixtures, for example tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.
In einer bevorzugten Ausführungsform enthält die erfindungsgemäße Mischung als Komponente (b) mindestens ein öllösliches Säureamid aus aliphatischen Polyaminen mit 2 bis 6 Stickstoffatomen und C16- bis C20-Fettsäuren, wobei alle primären und sekundären Aminofunktionen der Polyamine in Säureamidfunktionen übergeführt sind.In a preferred embodiment, the mixture according to the invention contains as component (b) at least one oil-soluble acid amide of aliphatic polyamines having 2 to 6 nitrogen atoms and C 16 - to C 20 -fatty acids, all primary and secondary amino functions of the polyamines being converted into acid amide functions.
Ein typisches Beispiel für ein öllösliches Säureamid der Komponente (b) ist das Umsetzungsprodukt von 3 Mol Ölsäure mit 1 Mol Diethylentriamin.A typical example of an oil-soluble acid amide of component (b) is the reaction product of 3 moles of oleic acid with 1 mole of diethylenetriamine.
Die den öllöslichen Umsetzungsprodukten der Komponente (c) zugrundeliegenden α,β-Dicarbonsäuren mit 4 bis 300, insbesondere 4 bis 75, vor allem 4 bis 12 Kohlenstoffatomen, sind üblicherweise Bernsteinsäure, Maleinsäure, Fumarsäure oder Derivate hiervon, die an der verbrückenden Ethylen- bzw. Ethenylen-Gruppe kürzer- oder längerkettige Hydrocarbyl-Substitutenten aufweisen können, welche Heteroatome und/oder funktionelle Gruppen enthalten bzw. tragen können. Für die Umsetzung mit den primären Alkylaminen werden diese in der Regel in Form der freien Dicarbonsäure oder deren reaktiver Derivate eingesetzt. Als reaktive Derivate können hier Carbonsäurehalogenide, Carbonsäureester oder insbesondere Carbonsäureanhydride eingesetzt werden.The oil-soluble reaction products of component (c) underlying α, β-dicarboxylic acids having 4 to 300, especially 4 to 75, especially 4 to 12 carbon atoms, are usually succinic acid, maleic acid, fumaric acid or derivatives thereof, at the bridging ethylene or Ethenylene group may have shorter or longer chain hydrocarbyl substituents which contain or may carry heteroatoms and / or functional groups. For the reaction with the primary alkylamines, these are generally used in the form of the free dicarboxylic acid or its reactive derivatives. Carboxylic acid halides, carboxylic acid esters or, in particular, carboxylic acid anhydrides can be used here as reactive derivatives.
In einer bevorzugten Ausführungsform enthält die erfindungsgemäße Mischung als Komponente (c) mindestens ein öllösliches Umsetzungsprodukt aus Maleinsäureanhydrid und primären Alkylaminen.In a preferred embodiment, the mixture according to the invention contains as component (c) at least one oil-soluble reaction product of maleic anhydride and primary alkylamines.
Die den öllöslichen Umsetzungsprodukten der Komponente (c) zugrundeliegenden primären Alkylamine sind üblicherweise mittelkettige oder langkettige Alkylmonoamine mit vorzugsweise 8 bis 30, insbesondere 12 bis 22 Kohlenstoffatomen, und linearer oder verzweigter, gesättigter oder ungesättigter Alkylkette, beispielsweise Octyl-, Nonyl-, iso-Nonyl-, Decyl-, Undecyl-, Tridecyl-, iso-Tridecyl-, Tetradecyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecylamin sowie Gemische solcher Amine. Sollen als derartige primäre Alkylamine natürlich vorkommende Fettamine eingesetzt werden, eignen sich vor allem Kokosamin, Talgfettamin, Oleylamin, Arachidylamin oder Behenylamin sowie Gemische hieraus. Die Umsetzungsprodukte der Komponente (c) liegen üblicherweise - je nach Stöchiometrie und Reaktionsführung - als Halb- oder Bisamide der Maleinsäure vor; sie können auch untergeordnete Menge an entsprechenden Ammoniumsalzen enthalten. Die Herstellung der öllöslichen Umsetzungsprodukte der Komponente (c) aus Maleinsäureanhydrid und primären Alkylaminen wird in Dokument (1) beschrieben.The primary alkylamines underlying the oil-soluble reaction products of component (c) are usually medium-chain or long-chain alkyl monoamines preferably having 8 to 30, in particular 12 to 22 carbon atoms, and linear or branched, saturated or unsaturated alkyl chain, for example octyl, nonyl, iso-nonyl -, decyl, undecyl, tridecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylamine and mixtures of such amines. Should be used as such primary alkyl amines naturally occurring fatty amines, especially coconut amine, tallow fatty amine, oleylamine, arachidylamine or behenyl amine and mixtures thereof are suitable. The reaction products of component (c) are usually - depending on the stoichiometry and reaction regime - as half or bisamides of maleic acid before; they may also contain minor amount of corresponding ammonium salts. The preparation of the oil-soluble reaction products of component (c) from maleic anhydride and primary alkylamines is described in document (1).
Ein typisches Beispiel für ein öllösliches Umsetzungsprodukt der Komponente (c) ist das Umsetzungsprodukt von 1 Mol Maleinsäureanhydrid mit 1 Mol iso-Tridecylamin, welches überwiegend als Halbamid der Maleinsäure vorliegt.A typical example of an oil-soluble reaction product of component (c) is the reaction product of 1 mol of maleic anhydride with 1 mol of iso-tridecylamine, which is present predominantly as a half-amide of maleic acid.
Die erfindungsgemäße Mischung kann durch einfaches Vermischen, gegebenenfalls in einem geeigneten Lösungsmittel, der Komponenten (a) und (b) bzw. (a) bis (c) ohne Wärmezufuhr hergestellt werden.The mixture according to the invention can be prepared by simple mixing, optionally in a suitable solvent, of components (a) and (b) or (a) to (c) without heat input.
Wird die Komponente (c) nicht mitverwendet, enthält die erfindungsgemäße Mischung die Komponenten (a) und (b) vorzugsweise in folgenden Verhältnissen, wobei die Summe dieser beiden Komponenten jeweils 100 Gew.-% ergibt:
- (a) 50 bis 95 Gew.-%, insbesondere 55 bis 85 Gew.-%, vor allem 60 bis 70 Gew.-%;
- (b) 5 bis 50 Gew.-%, insbesondere 15 bis 45 Gew.-%, vor allem 30 bis 40 Gew.-%.
- (A) 50 to 95 wt .-%, in particular 55 to 85 wt .-%, especially 60 to 70 wt .-%;
- (B) 5 to 50 wt .-%, in particular 15 to 45 wt .-%, especially 30 to 40 wt .-%.
Wird die Komponente (c) mitverwendet, enthält die erfindungsgemäße Mischung die Komponenten (a) bis (c) vorzugsweise in folgenden Verhältnissen, wobei die Summe aller drei Komponenten jeweils 100 Gew.-% ergibt:
- (a) 50 bis 85 Gew.-%, insbesondere 55 bis 75 Gew.-%, vor allem 60 bis 70 Gew.-%;
- (b) 10 bis 40 Gew.-%, insbesondere 15 bis 35 Gew.-%, vor allem 20 bis 30 Gew.-%;
- (c) 1 bis 25 Gew.-%, insbesondere 5 bis 20 Gew.-%, vor allem 10 bis 20 Gew.-%.
- (A) 50 to 85 wt .-%, in particular 55 to 75 wt .-%, especially 60 to 70 wt .-%;
- (B) 10 to 40 wt .-%, in particular 15 to 35 wt .-%, especially 20 to 30 wt .-%;
- (C) 1 to 25 wt .-%, in particular 5 to 20 wt .-%, especially 10 to 20 wt .-%.
Die erfindungsgemäße Mischung eignet sich als Zusatz zu Kraftstoffen, speziell Mitteldestillat-Kraftstoffen. Mitteldestillat-Kraftstoffe, die insbesondere als Gasöle, Petroleum, Dieselöle (Dieselkraftstoffe) oder leichte Heizöle Verwendung finden, werden oft auch als Brennstofföle bezeichnet. Derartige Mitteldestillat-Kraftstoffe weisen in der Regel Siedetemperaturen von 150 bis 400°C auf.The mixture according to the invention is suitable as an additive to fuels, especially middle distillate fuels. Middle distillate fuels, which are used in particular as gas oils, petroleum, diesel oils (diesel fuels) or light fuel oils, are often referred to as fuel oils. Such middle distillate fuels generally have boiling temperatures of 150 to 400 ° C.
Die erfindungsgemäße Mischung kann den Kraftstoffen direkt, d.h. unverdünnt, bevorzugt jedoch als 10 bis 70 gew.-%ige, insbesondere als 30 bis 65 gew.-%ige, vor allem als 45 bis 60 gew.-%ige Lösung (Konzentrat) in einem geeigneten Lösungsmittel, üblicherweise einem Kohlenwasserstoff-Lösungsmittel, zugesetzt werden. Ein solches Konzentrat, enthaltend 10 bis 70 Gew.-%, insbesondere 30 bis 65 Gew.-%, vor allem 45 bis 60 Gew.-%, bezogen auf die Gesamtmenge des Konzentrates, der erfindungsgemäßen Mischung, gelöst in einem Kohlenwasserstoff-Lösungsmittel, ist daher auch Gegenstand der vorliegenden Erfindung. Gängige Lösungsmittel sind in diesem Zusammenhang aliphatischen oder aromatische Kohlenwasserstoffe, beispielsweise Xylole oder Gemische hochsiedender Aromaten wie Solvent Naphtha. Auch Mitteldestillat-Kraftstoffe selbst können als Lösungsmittel für derartige Konzentrate verwendet werden.The mixture according to the invention can be injected directly into the fuels, i. undiluted, but preferably as 10 to 70 wt .-%, in particular as 30 to 65 wt .-%, especially as 45 to 60 wt .-% solution (concentrate) in a suitable solvent, usually a hydrocarbon solvent be added. Such a concentrate, containing 10 to 70 wt .-%, in particular 30 to 65 wt .-%, especially 45 to 60 wt .-%, based on the total amount of the concentrate, the mixture according to the invention, dissolved in a hydrocarbon solvent, is therefore also the subject of the present invention. Common solvents in this context are aliphatic or aromatic hydrocarbons, for example xylenes or mixtures of high-boiling aromatics such as solvent naphtha. Even middle distillate fuels themselves can be used as solvents for such concentrates.
Die Dosierrate der Mischung in den Kraftstoffen beträgt in der Regel 10 bis 10.000 Gew.-ppm, insbesondere 50 bis 5000 Gew.-ppm, vor allem 50 bis 1000 Gew.-ppm, z.B. 150 bis 400 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Mitteldestillat-Kraftstoff.The metering rate of the mixture in the fuels is generally 10 to 10,000 ppm by weight, in particular 50 to 5000 ppm by weight, especially 50 to 1000 ppm by weight, e.g. 150 to 400 ppm by weight, based in each case on the total amount of middle distillate fuel.
In einer bevorzugten Ausführungsform wird die erfindungsgemäße Mischung als Zusatz zu Kraftstoffen verwendet, welche
- (A) zu 0,1 bis 75 Gew.-%, vorzugsweise zu 0,5 bis 50 Gew.-%, insbesondere zu 1 bis 25 Gew.-%, vor allem zu 3 bis 12 Gew.-%, aus mindestens einem Biobrennstofföl, welches auf Fettsäureestern basiert, und
- (B) zu 25 bis 99,9 Gew.-%, vorzugsweise zu 50 bis 99,5 Gew.-%, insbesondere zu 75 bis 99 Gew.-%, vor allem zu 88 bis 97 Gew.-%, aus Mitteldestillaten aus fossilem Ursprung und/oder aus pflanzlichem und/oder tierischem Ursprung, welche im wesentlichen Kohlenwasserstoffmischungen darstellen und frei von Fettsäureestern sind,
- (A) to 0.1 to 75 wt .-%, preferably to 0.5 to 50 wt .-%, in particular to 1 to 25 wt .-%, especially to 3 to 12 wt .-%, of at least one Biofuel oil based on fatty acid esters, and
- (B) from 25 to 99.9% by weight, preferably from 50 to 99.5% by weight, in particular from 75 to 99% by weight, in particular from 88 to 97% by weight, of middle distillates of fossil origin and / or of vegetable and / or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters,
Die Kraftstoff-Komponente (A) wird meist auch als "Biodiesel" bezeichnet. Bei den Mitteldestillaten der Kraftstoff-Komponente (A) handelt es sich vorzugsweise im wesentlichen um Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere C1- bis C4-Alkylester, verstanden, die durch Umesterung der in pflanzlichen und/oder tierischen Ölen und/oder Fetten vorkommenden Glyceride, insbesondere Triglyceride, mittels Niedrigalkoholen, beispielsweise Ethanol, n-Propanol, isoPropanol, n-Butanol, iso-Butanol, sec.-Butanol, tert.-Butanol oder insbesondere Methanol ("FAME"), erhältlich sind.The fuel component (A) is usually referred to as "biodiesel". The middle distillates of the fuel component (A) are preferably substantially alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, in particular C 1 - to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, such as ethanol, n-propanol, isoPropanol , n-butanol, iso-butanol, sec-butanol, tert-butanol, or especially methanol ("FAME").
Beispiele für pflanzliche Öle, die in entsprechende Alkylester umgewandelt werden und somit als Basis für Biodiesel dienen können, sind Rizinusöl, Olivenöl, Erdnussöl, Palmkernöl, Kokosöl, Senföl, Baumwollsamenöl sowie insbesondere Sonnenblumenöl, Palmöl, Sojaöl und Rapsöl. Weitere Beispiele schließen Öle ein, die sich aus Weizen, Jute, Sesam und der Scheabaumnuß gewinnen lassen; weiterhin sind auch Arachisöl, Jatrophaöl und Leinöl verwendbar. Die Gewinnung dieser Öle und deren Umwandlung in die Alkylester sind aus dem Stand der Technik bekannt oder können daraus abgeleitet werden.Examples of vegetable oils which are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil, and in particular sunflower oil, palm oil, soybean oil and rapeseed oil. Other examples include oils that can be extracted from wheat, jute, sesame and the shea nut; furthermore, arachis oil, jatropha oil and linseed oil are also usable. The recovery of these oils and their conversion to the alkyl esters are known in the art or may be derived therefrom.
Es können auch schon verwendete pflanzliche Öle, beispielsweise gebrauchtes Frittieröl, gegebenenfalls nach einer entsprechenden Reinigung, in Alkylester umgewandelt werden und somit als Basis für Biodiesel dienen.It is also possible to convert already used vegetable oils, for example used frying oil, if appropriate after appropriate purification, into alkyl esters and thus serve as the basis for biodiesel.
Pflanzliche Fette sind ebenfalls im Prinzip als Quelle für Biodiesel verwendbar, spielen jedoch eine untergeordnete Rolle.Vegetable fats are also useful in principle as a source of biodiesel, but play a minor role.
Beispiele für tierische Fette und Öle, die in entsprechende Alkylester umgewandelt werden und somit als Basis für Biodiesel dienen können, sind Fischöl, Rindertalg, Schweinetalg und ähnliche beim Schlachten oder Verwerten von Nutz- oder Wildtieren als Abfälle anfallende Fette und Öle.Examples of animal fats and oils that are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are fish oil, beef tallow, Pig tallow and similar fats and oils derived from the slaughtering or recycling of farmed or wild animals.
Als den genannten pflanzlichen und/oder tierischen Ölen und/oder Fetten zugrundeliegenden gesättigte oder ungesättigte Fettsäuren, die meist von 12 bis 22 Kohlenstoffatome aufweisen und zusätzliche funktionelle Gruppe wie Hydroxylgruppen tragen können, treten in den Alkylestern insbesondere Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Linolsäure, Linolensäure, Elaidinsäure, Erucasäure und Ricinolsäure, insbesondere in Form von Mischungen solcher Fettsäuren, auf.As the said vegetable and / or animal oils and / or fats underlying saturated or unsaturated fatty acids, which usually have from 12 to 22 carbon atoms and may carry additional functional group such as hydroxyl groups, occur in the alkyl esters in particular lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid , Linoleic, linolenic, elaidic, erucic and ricinolic acids, especially in the form of mixtures of such fatty acids.
Typische Niedrigalkylester auf Basis von pflanzlichen und/oder tierischen Ölen und/oder Fetten, die als Biodiesel oder Biodiesel-Komponenten Verwendung finden, sind beispielsweise Sonnenblumenmethylester, Palmölmethylester ("PME"), Sojaölmethylester ("SME") und insbesondere Rapsölmethylester ("RME").Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biodiesel or biodiesel components are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and especially rapeseed oil methyl ester ("RME"). ).
Es können jedoch auch die Monoglyceride, Diglyceride und insbesondere Triglyceride selbst, beispielsweise Rizinusöl, oder Mischungen aus solchen Glyceriden als Biodiesel oder Komponenten für Biodiesel eingesetzt werden.However, it is also possible to use the monoglycerides, diglycerides and especially triglycerides themselves, for example castor oil, or mixtures of such glycerides as biodiesel or components for biodiesel.
Unter der Kraftstoff-Komponente (B) sollen im Rahmen der vorliegenden Erfindung im Bereich von 120 bis 450°C siedende Mitteldestillat-Kraftstoffe verstanden werden. Solche Mitteldestillat-Kraftstoffe werden insbesondere als Dieselkraftstoff, Heizöl oder Kerosin verwendet, wobei Dieselkraftstoff und Heizöl besonders bevorzugt sind.For the purposes of the present invention, fuel component (B) is to be understood to mean boiling middle distillate fuels in the range from 120 to 450 ° C. Such middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
Mit Mitteldestillat-Kraftstoffen werden Kraft- und Brennstoffe bezeichnet, die durch Destillation von Rohöl gewonnen werden und im Bereich von 120 bis 450°C sieden. Vorzugsweise werden schwefelarme Mitteldestillate verwendet, d.h. solche, die weniger als 350 ppm Schwefel, insbesondere weniger als 200 ppm Schwefel, vor allem weniger als 50 ppm Schwefel enthalten. In speziellen Fällen enthalten sie weniger als 10 ppm Schwefel, diese Mitteldestillate werden auch als "schwefelfrei" bezeichnet. Es handelt sich dabei im allgemeinen um Rohöldestillate, die einer hydrierenden Raffination unterworfen wurden, und die daher nur geringe Anteile an polyaromatischen und polaren Verbindungen enthalten. Vorzugsweise handelt es sich um solche Mitteldestillate, die 95%-Destillationspunkte unter 370°C, insbesondere unter 350°C und in Spezialfällen unter 330°C aufweisen.Middle distillate fuels are fuels obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C. Preferably, low sulfur middle distillates are used, i. those containing less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur, especially less than 50 ppm of sulfur. In special cases they contain less than 10 ppm sulfur, these middle distillates are also called "sulfur-free". These are generally crude oil distillates, which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds. These are preferably middle distillates which have 95% distillation points below 370 ° C., in particular below 350 ° C. and in special cases below 330 ° C.
Schwefelarme und schwefelfreie Mitteldestillate können auch aus schwereren Erdölfraktionen gewonnen werden, die nicht mehr unter Atmosphärendruck destilliert werden können. Als typische Konversionsverfahren zur Herstellung von Mitteldestillaten aus schweren Erdölfraktionen seien genannt: Hydrocracken, thermisches Cracken, katalytisches Cracken, Cokerprozesse und/oder Visbreaking. Je nach Verfahrensdurchführung fallen diese Mitteldestillate schwefelarm oder schwefelfrei an oder werden einer hydrierenden Raffination unterworfen.Low-sulfur and sulfur-free middle distillates can also be obtained from heavier petroleum fractions, which can no longer be distilled under atmospheric pressure. Hydrocarbon cracking, thermal cracking, catalytic cracking, coker processes and / or visbreaking may be mentioned as typical conversion processes for the preparation of middle distillates from heavy petroleum fractions. Depending on the procedure These middle distillates fall to low sulfur or sulfur-free or are subjected to a hydrogenating refining.
Vorzugsweise haben die Mitteldestillate Aromatengehalte von unter 28 Gew.-%, insbesondere unter 20 Gew.-%. Der Gehalt an Normalparaffinen beträgt zwischen 5% und 50 Gew.-%, vorzugsweise liegt er zwischen 10 und 35 Gew.%.The middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight. The content of normal paraffins is between 5% and 50% by weight, preferably between 10 and 35% by weight.
Unter den als Kraftstoff-Komponente (B) bezeichneten Mitteldestillaten sollen hier auch Mitteldestillate verstanden werden, welche sich entweder indirekt von fossilen Quellen wie Erdöl oder Erdgas ableiten lassen oder aber aus Biomasse über Vergasung und anschließende Hydrierung hergestellt werden. Ein typisches Beispiel für einen sich indirekt von fossilen Quellen ableitenden Mitteldestillat-Kraftstoff ist der mittels Fischer-Tropsch-Synthese erzeugte GTL("gas-to-liquid")-Dieselkraftstoff. Aus Biomasse wird beispielweise über den BTL("bio-to-liquid")-Prozeß ein Mitteldestillat hergestellt, das entweder allein oder in Mischung mit anderen Mitteldestillaten als Kraftstoffkomponente (B) verwendet werden kann. Zu den Mitteldestillaten gehören auch Kohlenwasserstoffe, die durch Hydrierung von Fetten und Fettölen gewonnen werden. Sie enthalten überwiegend n-Paraffine. Den genannten Mitteldestillat-Kraftstoffen ist gemeinsam, dass sie im wesentlichen Kohlenwasserstoffmischungen darstellen und frei von Fettsäureestern sind.Among the middle distillates referred to as fuel component (B), middle distillates should also be understood here, which can be derived either indirectly from fossil sources such as crude oil or natural gas or else produced from biomass via gasification and subsequent hydrogenation. A typical example of a middle distillate fuel derived indirectly from fossil sources is GTL (gas-to-liquid) diesel fuel produced by Fischer-Tropsch synthesis. From biomass, for example, a middle distillate is produced via the BTL ("bio-to-liquid") process, which can be used either alone or in admixture with other middle distillates as fuel component (B). The middle distillates also include hydrocarbons obtained by hydrogenation of fats and fatty oils. They contain mostly n-paraffins. The said middle distillate fuels have in common that they are essentially hydrocarbon mixtures and are free from fatty acid esters.
Die Qualitäten der Heizöle und Dieselkraftstoffe sind beispielsweise in DIN 51603 und EN 590 näher festgelegt (vgl. auch Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, Band A12, S. 617 ff., worauf hiermit ausdrücklich Bezug genommen wird).The qualities of fuel oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, pp. 617 et seq., To which reference is expressly made).
Die erfindungsgemäße Mischung wird in den genannten Kraftstoffen vorrzugsweise in der Funktion als Paraffindispergator ("WASA") verwendet. Die erfindungsgemäße Mischung entfaltet ihre Wirkung als Paraffindispergator oft besonders gut erst zusammen mit den üblichen Fließverbesserern.The mixture according to the invention is preferably used in the said fuels as a paraffin dispersant ("WASA"). The mixture according to the invention often unfolds its action as paraffin dispersant only particularly well together with the customary flow improvers.
Unter Fließverbesserern sollen im Rahmen der vorliegenden Erfindung alle Additive verstanden werden, die die Kälteeigenschaften von Mitteldestillat-Kraftstoffen verbessern. Neben den eigentlichen Kaltfließverbesserern ("MDFI") sind dies auch Nukleatoren (vgl. auch Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, Band A16, S. 719 ff.).In the context of the present invention, flow improvers are to be understood as meaning all additives which improve the cold properties of middle distillate fuels. In addition to the actual cold flow improvers ("MDFI"), these are also nucleators (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A16, page 719 ff.).
Die erfindungsgemäßen Mitteldestillat-Kraftstoffe enthalten neben der erfindungsgemäßen Mischung beim Vorliegen von Kaltfließverbesserern diese in einer Menge von üblicherweise 1 bis 2000 Gew.-ppm, vorzugsweise von 5 bis 1000 Gew.-ppm, insbesondere von 10 bis 750 Gew.-ppm und vor allem von 50 bis 500 Gew.-ppm, z.B. von 150 bis 400 Gew.-ppm.The middle distillate fuels according to the invention contain in addition to the mixture according to the invention in the presence of cold flow improvers these in an amount of usually 1 to 2000 ppm by weight, preferably from 5 to 1000 ppm by weight, especially from 10 to 750 ppm by weight and especially from 50 to 500 ppm by weight, for example from 150 to 400 ppm by weight.
Als derartige Kaltfließverbesserer kommen insbesondere für die Kombination mit der erfindungsgemäßen Mischung einer oder mehrere der nachfolgend genannten in Betracht, die übliche Vertreter für den Einsatz in Mitteldestillat-Kraftstoffen darstellen:
- (d) Copolymere von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
- (e) Kammpolymere;
- (f) Polyoxyalkylene;
- (g) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten;
- (h) Poly(meth)acrylsäureester
- (d) copolymers of ethylene with at least one other ethylenically unsaturated monomer;
- (e) comb polymers;
- (f) polyoxyalkylenes;
- (g) sulfocarboxylic acids or sulfonic acids or their derivatives;
- (h) poly (meth) acrylic ester
Bei den Copolymeren von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer der Gruppe (d) ist das Monomer vorzugsweise ausgewählt unter Alkenylcarbonsäureestern, (Meth)Acrylsäureestern und Olefinen.In the copolymers of ethylene with at least one other ethylenically unsaturated monomer of group (d), the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters and olefins.
Geeignete Olefine sind beispielsweise solche mit 3 bis 10 Kohlenstoffatomen sowie mit 1 bis 3, vorzugsweise mit 1 oder 2, insbesondere mit einer Kohlenstoff-Kohlenstoff-Doppelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (α-Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α-Olefine, besonders bevorzugt α-Olefine mit 3 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1-Buten, 1-Penten und 1-Hexen.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. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 3 to 6 carbon atoms, for example propene, 1-butene, 1-pentene and 1-hexene.
Geeignete (Meth)Acrylsäureester sind beispielsweise Ester der (Meth)Acrylsäure mit C1- bis C10-Alkanolen, insbesondere mit Methanol, Ethanol, Propanol, Isopropanol, n-Butanol, sec.-Butanol, Isobutanol, tert.-Butanol, Pentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol und Decanol.Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 - to C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
Geeignete Alkenylcarbonsäureester sind beispielsweise die Vinyl- und Propenylester von Carbonsäuren mit 2 bis 20 Kohlenstoffatomen, deren Kohlenwasserstoffrest linear oder verzweigt sein kann. Bevorzugt sind hierunter die Vinylester. Unter den Carbonsäuren mit verzweigtem Kohlenwasserstoffrest sind solche bevorzugt, deren Verzweigung sich in der α-Position zur Carboxylgruppe befindet, wobei das α-Kohlenstoffatom besonders bevorzugt tertiär ist, d. h. die Carbonsäure eine sogenannte Neocarbonsäure ist. Vorzugsweise ist der Kohlenwasserstoffrest der Carbonsäure jedoch linear.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. Among the carboxylic acids having a branched hydrocarbon radical, preferred are those whose branch is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.
Beispiele für geeignete Alkenylcarbonsäureester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Neopentansäurevinylester, Hexansäurevinylester, Neononansäurevinylester, Neodecansäurevinylester und die entsprechenden Propenylester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Alkenylcarbonsäureester ist Vinylacetat; typische hieraus resultierende Copolymere der Gruppe (d) sind Ethylen-Vinylacetat-Copolymere ("EVA"), welche in großem Umfang in Dieselkraftstoffen eingesetzt werden.Examples of suitable alkenylcarboxylic esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate; typical copolymers of group (d) resulting therefrom are ethylene-vinyl acetate copolymers ("EVA"), which are widely used in diesel fuels.
Besonders bevorzugt ist das ethylenisch ungesättigte Monomer ausgewählt unter Alkenylcarbonsäureestern.Particularly preferably, the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.
Geeignet sind auch Copolymere, die zwei oder mehrere voneinander verschiedene Alkenylcarbonsäureester einpolymerisiert enthalten, wobei diese sich in der Alkenylfunktion und/oder in der Carbonsäuregruppe unterscheiden. Ebenfalls geeignet sind Copolymere, die neben dem/den Alkenylcarbonsäureester(n) wenigstens ein Olefin und/oder wenigstens ein (Meth)Acrylsäureester einpolymerisiert enthalten.Also suitable are 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. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
Das ethylenisch ungesättigte Monomer ist im Copolymer der Gruppe (d) in einer Menge von vorzugsweise 1 bis 50 Mol.-%, insbesondere von 10 bis 50 Mol.-% und vor allem von 5 bis 20 Mol.-%, bezogen auf das Gesamtcopolymer, einpolymerisiert.The ethylenically unsaturated monomer is in the copolymer of group (d) in an amount of preferably 1 to 50 mol .-%, in particular from 10 to 50 mol .-% and especially from 5 to 20 mol .-%, based on the total copolymer , copolymerized.
Das Copolymer der Gruppe (d) weist vorzugsweise ein zahlenmittleres Molekulargewicht Mn von 1000 bis 20.000, besonders bevorzugt von 1000 bis 10.000 und insbesondere von 1000 bis 6000 auf.The copolymer of group (d) preferably has a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.
Kammpolymere der Gruppe (e) sind beispielsweise solche, die in "
- D für R17, COOR17, OCOR17, R18, OCOR17 oder OR17 steht,
- E für H, CH3, D oder R18 steht,
- G für H oder D steht,
- J für H, R18, R18COOR17, Aryl oder Heterocyclyl steht,
- K für H, COOR18, OCOR18, OR18 oder COOH steht,
- L für H, R18 COOR18, OCOR18, COOH oder Aryl steht,
- R17 für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
- R18 für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
- m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
- n für einen Molenbruch im Bereich von 0 bis 0,6 steht.
- 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 , 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,
- 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 0 to 0.6.
Bevorzugte Kammpolymere sind beispielsweise durch die Copolymerisation von Maleinsäureanhydrid oder Fumarsäure mit einem anderen ethylenisch ungesättigten Monomer, beispielsweise mit einem α-Olefin oder einem ungesättigten Ester wie Vinylacetat, und anschließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere bevorzugte Kammpolymere sind Copolymere von α-Olefinen und veresterten Comonomeren, beispielsweise veresterte Copolymere von Styrol und Maleinsäureanhydrid oder veresterte Copolymere von Styrol und Fumarsäure. Auch Gemische von Kammpolymeren sind geeignet. Kammpolymere können auch Polyfumarate oder Polymaleinate sein. Außerdem sind Homo- und Copolymere von Vinylethern geeignete Kammpolymere.Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Other preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Also mixtures of comb polymers are suitable. Comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers.
Geeignete Polyoxyalkylene der Gruppe (f) sind beispielsweise Polyoxyalkylenester, -ether, -ester/ether und Gemische davon. Bevorzugt enthalten die Polyoxyalkylenverbindungen wenigstens eine, besonders bevorzugt wenigstens zwei lineare Alkylgruppen mit jeweils 10 bis 30 Kohlenstoffatomen und eine Polyoxyalkylengruppe mit einem Molekulargewicht von bis zu 5000. Die Alkylgruppe des Polyoxyalkylenrestes enthält dabei vorzugsweise 1 bis 4 Kohlenstoffatome. Derartige Polyoxyalkylenverbindungen sind beispielsweise in der
R19[-O-(CH2)y]xO-R20 (V)
worin
- R19 und R20 jeweils unabhängig voneinander für R21, R21-CO-, R21-O-CO(CH2)2- oder R21-O-CO(CH2)z-CO- stehen, wobei R21 für lineares C1-C30-Alkyl steht,
- y für eine Zahl von 1 bis 4 steht,
- x für eine Zahl von 2 bis 200 steht, und
- z für eine Zahl von 1 bis 4 steht.
R 19 [-O- (CH 2 ) y ] x OR 20 (V)
wherein
- R 19 and R 20 are each independently R 21 , R 21 is CO, R 21 is -O-CO (CH 2 ) 2 - or R 21 is -O-CO (CH 2 ) z -CO-, wherein R 21 is linear C 1 -C 30 -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.
Bevorzugte Polyoxyalkylenverbindungen der Formel V, in denen sowohl R19 als auch R20 für R21 stehen, sind Polyethylenglykole und Polypropylenglykole mit einem zahlenmittleren Molekulargewicht von 100 bis 5000. Bevorzugte Polyoxyalkylene der Formel V, in denen einer der Reste R19 für R21 und der andere für R21-CO- steht, sind Polyoxyalkylenester von Fettsäuren mit 10 bis 30 Kohlenstoffatomen wie Stearinsäure oder Behensäure. Bevorzugte Polyoxyalkylenverbindungen, in denen sowohl R19 als auch R20 für einen Rest R21-CO- stehen, sind Diester von Fettsäuren mit 10 bis 30 Kohlenstoffatomen, bevorzugt von Stearin- oder Behensäure.Preferred polyoxyalkylene compounds of the formula V 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 V 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.
Geeignete Sulfocarbonsäuren/Sulfonsäuren bzw. deren Derivate der Gruppe (g) sind beispielsweise solche der allgemeinen Formel VI
- Y' für SO3 -(NR25 3R26)+, SO3 -(NHR25 2R26)+, SO3-(NH2R25R26), SO3-(NH3R26) oder SO2NR25R26 steht,
- X' für Y', CONR25R27, CO2 -(NR25 3R27)+, CO2 -(NHR25 2R27)+, R28-COOR27, NR27COR27, R28OR27, R28OCOR27, R28R27, N(COR25)R27 oder Z-(NR25 3R27)+ steht,
- R25 für einen Kohlenwasserstoffrest steht,
- R26 und R27 für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
- R28 für C2-C5-Alkylen steht,
- Z- für ein Anionenäquivalent steht und
- A" und B' für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.
- Y 'for 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 SO 2 NR 25 R 26 stands,
- X 'for Y', CONR 25 R 27 , CO 2 - (NR 25 3 R 27 ) + , CO 2 - (NHR 25 2 R 27 ) + , R 28 -COOR 27 , NR 27 COR 27 , R 28 OR 27 , R 28 OCOR 27 , R 28 R 27 , N (COR 25 ) R 27 or Z - (NR 25 3 R 27 ) + ,
- 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,
- Z- represents an anion equivalent and
- 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.
Derartige Sulfocarbonsäuren bzw. Sulfonsäuren und ihre Derivate sind in der
Geeignete Poly(meth)acrylsäureester der Gruppe (h) sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäureestern. Bevorzugt sind Copolymere von wenigstens zwei voneinander verschiedenen (Meth)Acrylsäureestern, die sich bezüglich des einkondensierten Alkohols unterscheiden. Gegebenenfalls enthält das Copolymer noch ein weiteres, davon verschiedenes olefinisch ungesättigtes Monomer einpolymerisiert. Das gewichtsmittlere Molekulargewicht des Polymers beträgt vorzugsweise 50.000 bis 500.000. Ein besonders bevorzugtes Polymer ist ein Copolymer von Methacrylsäure und Methacrylsäureestern von gesättigten C14- und C15-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der
Mit üblichen Fließverbesserern - beispielsweise Ethylen-Vinylacetat-Copolymeren aus der Gruppe (d), wie sie in der
Ebenso können durch die Verwendung der erfindungsgemäßen Mischung eine Reihe weitere Kraftstoffeigenschaften verbessert werden. Exemplarisch sollen hier nur die zusätzliche Wirkung als Korrosionsschutz oder die Verbesserung der Oxidationsstabilität genannt werden.Likewise, by using the mixture according to the invention a number of other fuel properties can be improved. By way of example, only the additional effect of protecting against corrosion or improving the stability to oxidation should be mentioned here.
Bei Einsatz in schwefelarmen Kraftstoffen, die überwiegend oder allein die Komponente (B) enthalten, kann der Einsatz der erfindungsgemäßen Mischung, insbesondere in Kombination mit Fließverbesserern, zu einer Verbesserung der Schmierwirkung beitragen. Die Schmierwirkung wird dabei beispielsweise im sog. HFRR-Test gemäß ISO 12156 bestimmt.When used in low-sulfur fuels containing component (B) predominantly or solely, the use of the mixture according to the invention, in particular in combination with flow improvers, can contribute to an improvement in the lubricating effect. The lubricating effect is determined, for example, in the so-called HFRR test according to ISO 12156.
Die erfindungsgemäße Mischung kann sowohl Mitteldestillat-Kraftstoffen, die vollständig fossilen Ursprungs sind, also aus Erdöl gewonnen wurden, als auch Kraftstoffen, die neben dem auf Erdöl basierenden Anteil einen Anteil an Biodiesel enthalten, zur Verbesserung deren Eigenschaften zugesetzt werden. In beiden Fällen wird eine deutliche Verbesserung des Kaltfließverhaltens des Mitteldestillat-Kraftstoffes, d.h. eine Absenkung der CP-Werte und/oder CFPP-Werte, unabhängig von der Herkunft oder der Zusammensetzung des Kraftstoffes beobachtet. Die ausgeschiedenen Paraffinkristalle werden wirksam in der Schwebe gehalten, so dass es nicht zu Verstopfungen von Filtern und Leitungen durch sedimentiertes Paraffin kommt. Die erfindungsgemäße Mischung weist eine gute Breitenwirkung auf und bewirkt so, dass die ausgeschiedenen Paraffinkristalle in den unterschiedlichsten Mitteldestillat-Kraftstoffen sehr gut dispergiert werden.The mixture according to the invention can be added both middle distillate fuels, which are completely fossil origin, that is, derived from petroleum, as well as fuels containing a proportion of biodiesel in addition to the petroleum-based portion, to improve their properties. In both cases, a significant improvement in the cold flow behavior of the middle distillate fuel, i. a reduction in CP values and / or CFPP values, regardless of the origin or composition of the fuel observed. The precipitated paraffin crystals are effectively kept in suspension, so that there is no clogging of filters and lines by sedimented paraffin. The mixture according to the invention has a good broad action and thus effects that the precipitated paraffin crystals are very well dispersed in the most varied middle distillate fuels.
Gegenstand der vorliegenden Erfindung sind auch Kraftstoffe, insbesondere solche mit einem Biodiesel-Anteil, die die erfindungsgemäße Mischung enthalten.The present invention also fuels, in particular those with a biodiesel content, which contain the mixture according to the invention.
In der Regel enthalten die genannten Kraftstoffe bzw. die genannten Kraftstoffadditiv-Konzentrate noch als weitere Zusätze in hierfür üblichen Mengen Fließverbesserer (wie oben beschrieben), weitere Paraffindispergatoren, Leitfähigkeitsverbesserer, Korrosionsschutzadditive, Lubricity-Additive, Antioxidantien, Metall-Deaktivatoren, Antischaummittel, Demulgatoren, Detergentien, Cetanzahl-Verbesserer, Lösungs- oder Verdünnungsmittel, Farbstoffe oder Duftstoffe oder Gemische davon. Die vorstehend genannten weiteren Zusätze, die oben noch nicht angesprochen worden sind, sind dem Fachmann geläufig und brauchen deshalb hier nicht weiter erläutert zu werden.As a rule, the fuels mentioned or the fuel additive concentrates mentioned contain further additives in customary amounts of flow improver (as described above), further paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, Detergents, cetane improvers, solvents or diluents, dyes or fragrances, or mixtures thereof. The abovementioned further additives, which have not yet been mentioned above, are familiar to the person skilled in the art and therefore need not be further explained here.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung erläutern, ohne sie zu beschränken.The following examples are intended to illustrate the present invention without limiting it.
- Komponente (a): mit 4 Mol hydriertem Ditalgfettamin umgesetzte Ethylendiamintetraessigsäure, hergestellt in Solvent Naphtha wie in Beispiel 1 des Dokumentes (1) beschrieben;Component (a): ethylenediaminetetraacetic acid reacted with 4 moles of hydrogenated di-tallow fatty amine prepared in solvent naphtha as described in Example 1 of document (1);
- Komponente (b): mit 3 Mol Ölsäure umgesetztes Diethylentriamin, hergestellt wie in Beispiel A 69 der Tabelle 1 des Dokumentes (2) beschrieben;Component (b): diethylenetriamine reacted with 3 moles of oleic acid prepared as described in Example A 69 of Table 1 of document (2);
- Komponente (c): mit 1 Mol Tridecylamim umgesetztes Maleinsäureanhydrid, hergestellt in Solvent Naphtha wie in Beispiel 2 des Dokumentes (1) beschrieben.Component (c): maleic anhydride reacted with 1 mol of tridecylamine, prepared in solvent naphtha as described in Example 2 of document (1).
Aus den oben genannten Komponenten (a) bis (c) wurden die folgenden Konzentrate K1 (erfindungsgemäß), K2 (zum Vergleich) und K3 (zum Vergleich) erstellt:
Die in Tabelle 1 angegebenen Mischungsverhältnisse sind Gew.-%; der Lösemittelgehalt dieser Mischungen betrug 40 Gew.-%, zusätzlich enthielten diese Mischungen noch 5% nicht die kaltfließverbessernde Wirkung beeinflussende übliche Zusätze.The mixing ratios given in Table 1 are% by weight; the solvent content of these mixtures was 40 wt .-%, in addition, these mixtures still contained 5% not the cold flow improving effect affecting conventional additives.
Die genannten deutschen Winter-Dieselkraftstoffe (DK1 bis DK7) sind durch folgende Parameter charakterisiert:
- DK1:
- CP (nach ISO 3015): -5,9°C, CFPP (nach EN 116): -9°C; Dichte d15 (DIN 51577): 837,5 kg/m3; Siedeanfang (DIN 51751): 178°C, Siedeende: 364°C; Paraffingehalt (gemäß GC): 16,6 Gew.-%
- DK2:
- CP (nach ISO 3015): -5,9°C, CFPP (nach EN 116): -7°C; Siedeanfang (DIN 51751): 180°C, Siedeende: 362°C; Paraffingehalt (gemäß GC): 16,6 Gew.-%
- DK3:
- CP (nach ISO 3015): -7,0°C, CFPP (nach EN 116): -8°C; Dichte d15 (DIN 51577): 831,6 kg/m3; Siedeanfang (DIN 51751): 170°C, Siedeende: 357°C; Paraffingehalt (gemäß GC): 22,1 Gew.-%
- DK4:
- CP (nach ISO 3015): -7,0°C, CFPP (nach EN 116): -9°C; Siedeanfang (DIN 51751): 172°C, Siedeende: 355°C; Paraffingehalt (gemäß GC): 22,2 Gew.-%
- DK5:
- CP (nach ISO 3015): -7,0°C, CFPP (nach EN 116): -9°C; Dichte d15 (DIN 51577): 828,9 kg/m3; Siedeanfang (DIN 51751): 176°C, Siedeende: 356°C; Paraffingehalt (gemäß GC): 22,1 Gew.-%
- DK6:
- CP (nach ISO 3015): -7,4°C, CFPP (nach EN 116): -7°C; Dichte d15 (DIN 51577): 827,8 kg/m3; Siedeanfang (DIN 51751): 169°C, Siedeende: 349°C; Paraffingehalt (gemäß GC): 21,8 Gew.-%
- DK7:
- CP (nach ISO 3015): -6,5°C, CFPP (nach EN 116): -8°C; Dichte d15 (DIN 51577): 824,1 kg/m3; Siedeanfang (DIN 51751): 182°C, Siedeende: 350°C; Paraffingehalt (gemäß GC): 23,3 Gew.-%
- DK1:
- CP (according to ISO 3015): -5.9 ° C, CFPP (according to EN 116): -9 ° C; Density d 15 (DIN 51577): 837.5 kg / m 3 ; Initial boiling point (DIN 51751): 178 ° C, boiling end: 364 ° C; Paraffin content (according to GC): 16.6% by weight
- DK2:
- CP (according to ISO 3015): -5.9 ° C, CFPP (according to EN 116): -7 ° C; Initial boiling point (DIN 51751): 180 ° C, boiling end: 362 ° C; Paraffin content (according to GC): 16.6% by weight
- DK3:
- CP (according to ISO 3015): -7.0 ° C, CFPP (according to EN 116): -8 ° C; Density d 15 (DIN 51577): 831.6 kg / m 3 ; Initial boiling point (DIN 51751): 170 ° C, boiling end: 357 ° C; Paraffin content (according to GC): 22.1% by weight
- DK 4:
- CP (according to ISO 3015): -7.0 ° C, CFPP (according to EN 116): -9 ° C; Initial boiling point (DIN 51751): 172 ° C, boiling end: 355 ° C; Paraffin content (according to GC): 22.2% by weight
- DK5:
- CP (according to ISO 3015): -7.0 ° C, CFPP (according to EN 116): -9 ° C; Density d 15 (DIN 51577): 828.9 kg / m 3 ; Initial boiling point (DIN 51751): 176 ° C, boiling end: 356 ° C; Paraffin content (according to GC): 22.1% by weight
- DK6:
- CP (according to ISO 3015): -7,4 ° C, CFPP (according to EN 116): -7 ° C; Density d 15 (DIN 51577): 827.8 kg / m 3 ; Initial boiling point (DIN 51751): 169 ° C, boiling end: 349 ° C; Paraffin content (according to GC): 21.8% by weight
- DK7:
- CP (according to ISO 3015): -6.5 ° C, CFPP (according to EN 116): -8 ° C; Density d 15 (DIN 51577): 824.1 kg / m 3 ; Initial boiling point (DIN 51751): 182 ° C, boiling end: 350 ° C; Paraffin content (according to GC): 23.3% by weight
Als Biodiesel-Zusätze wurden verwendet: Rapsölmethylester ("RME"), Sojaölmethylester ("SME") oder Palmölmethylester ("PME").As biodiesel additives were used: rapeseed oil methyl ester ("RME"), soybean oil methyl ester ("SME") or palm oil methyl ester ("PME").
Als Kaltfließverbesserer ("MDFI") wurden mitverwendet:
- FB1: handelsübliches Ethylen-Vinylacetat-Copolymer mit einem Vinylacetat-Gehalt von 30 Gew.-% gemäß Dokument (4);
- FB2: Mischung gemäß Dokument (5) aus einem handelsüblichen Ethylen-Vinylacetat-Copolymer und einem Hydrocarbylvinylether-Homopolymer mit Kammstruktur;
- FB1: commercial ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight according to document (4);
- FB2: Mixture according to document (5) of a commercial ethylene-vinyl acetate copolymer and a hydrocarbyl vinyl ether homopolymer having a comb structure;
FB1 und FB2 wurden aufgrund ihrer CFPP-Performance in den verwendeten Dieselkraftstoffen ausgewählt. Es ist sehr wahrscheinlich, dass andere Dieselkraftstoffe andere MDFI erfordern, Insofern sind die erfindungsgemäßen Mischungen nicht auf die Verwendung in Verbindung mit FB1 und FB2 beschränkt. In der im folgenden beschriebenen Versuchsdurchführung wurden die Additive K1 bis K3 und FB1 bzw. FB2 jeweils getrennt den Dieselkraftstoffen zugegeben. Es ist auch möglich, die Konzentrate K1, K2 und K3 zunächst mit den MDFI FB1 bzw. FB2 zu mischen und dann gemeinsam in die Dieselkraftstoffe DK1 bis DK 7 einzumischen.FB1 and FB2 were selected for their CFPP performance in the diesel fuels used. It is very likely that other diesel fuels will require other MDFI. Thus, the blends of the invention are not limited to use in conjunction with FB1 and FB2. In the experimental procedure described below, the additives K1 to K3 and FB1 or FB2 were each added separately to the diesel fuels. It is also possible to use the concentrates First mix K1, K2 and K3 with the MDFI FB1 or FB2 and then mix them together in the diesel fuels DK1 to DK7.
Die Kraftstoffe DK1 bis DK7 wurden mit den in der nachfolgenden Tabelle angegebenen Mengen an Biodiesel-Zusatz, dem Konzentrat K1, K2 oder K3 und dem Fließverbesserer FB1 oder FB2 versetzt, bei 40°C unter Rühren vermischt und anschließend auf Raumtemperatur abgekühlt. Von diesen additivierten Kraftstoffproben wurden der CP nach ISO 3015 und der CFPP nach EN 116 bestimmt. Danach wurden die additivierten Kraftstoffproben in 500 ml-Glaszylindern in einem Kältebad von Raumtemperatur mit einer Abkühlungsrate von ca. 14°C pro Stunde auf -13°C abgekühlt und 16 Stunden bei dieser Temperatur gelagert. Von der bei -13°C abgetrennten 20 Vol.-%-Bodenphase wurde von jeder Probe wiederum der CP nach ISO 3015 und der CFPP nach EN 116 ermittelt. Je geringer die Abweichung des CP der 20 Vol.-%-Bodenphase vom ursprünglichen CP der jeweiligen Kraftstoffprobe, desto besser sind die Paraffine dispergiert.The fuels DK1 to DK7 were admixed with the amounts of biodiesel additive specified in the table below, the concentrate K1, K2 or K3 and the flow improver FB1 or FB2, mixed with stirring at 40.degree. C. and then cooled to room temperature. Of these additized fuel samples, the CP was determined according to ISO 3015 and the CFPP according to EN 116. Thereafter, the additized fuel samples were cooled in 500 ml glass cylinders in a cold bath from room temperature at a cooling rate of about 14 ° C per hour to -13 ° C and stored for 16 hours at this temperature. From the 20% by volume soil phase separated at -13 ° C., the CP according to ISO 3015 and the CFPP according to EN 116 were again determined from each sample. The lower the deviation of the CP of the 20% by volume soil phase from the original CP of the respective fuel sample, the better the paraffins are dispersed.
Die erhaltenen Ergebnisse sind in der nachfolgenden Tabelle 2 aufgeführt:
Die Spalte 3 gibt Menge (in Gew.-%) und Typ des verwendeten Biodiesel-Zusatzes an.Column 3 indicates quantity (in wt.%) And type of biodiesel additive used.
Die Spalte 5 gibt die Dosiermenge des in der 4. Spalte genannten Fließverbesserers FB1 oder FB2 ("MDFI") in Gew.-ppm an.Column 5 indicates the metered quantity of the flow improver FB1 or FB2 ("MDFI") stated in the 4th column in ppm by weight.
Die Spalte 7 gibt die Dosiermenge des in der 6. Spalte genannten Paraffindispergators ("WASA") K1 (erfindungsgemäß) oder K2 (zum Vergleich) oder K3 (zum Vergleich) in Gew.-ppm an.Column 7 indicates the metered quantity of the paraffin dispersant ("WASA") K1 (according to the invention) or K2 (for comparison) or K3 (for comparison) mentioned in the 6th column in ppm by weight.
CP* (Spalte 8) und CFPP* (Spalte 11) geben die Werte der additivierten Kraftstoffproben vor dem Abkühlen an. CP# (Spalte 9) und CFPP# (Spalte 12) geben die entsprechenden Werte der nach dem Abkühlen jeweils abgetrennten 20 Vol.-%-Bodenphase an. Spalte 10 ist der Absolutwert der Differenz von CP# zu CP*.CP * (column 8) and CFPP * (column 11) indicate the values of the additized fuel samples before cooling. CP # (column 9) and CFPP # (column 12) indicate the corresponding values of the 20% by volume soil phase each separated after cooling. Column 10 is the absolute value of the difference from CP # to CP *.
Spalte 13 gibt die Vol.-% Sediment an Paraffin nach Lagerung im Kältebad bei -13°C an. Bewegt sich der angegebene Wert im unteren Bereich (im Falle der aufgeführten Beispiele unter 40 Vol.-%), gilt: je geringer der hier angegebene Wert ist, desto besser ist das Paraffin-Dispergierverhalten. Sehr hohe Werte in Spalte 13 (im Falle der aufgeführten Beispiele über 60 Vol.-%) sind allerdings ebenfalls ein Indiz für gutes Paraffin-Dispergierverhalten. Kritisch ist eine Paraffinsedimentation meist von ca. 10 bis 30 Vol.-%, da sich dann der größte Teil der ausgefallenen Paraffinkristalle in der 20 Vol.-%-Bodenphase befindet, die zur Charakterisierung der Wirksamkeit der Additive - wie beschrieben - verwendet wird.Column 13 indicates the vol .-% sediment of paraffin after storage in a cold bath at -13 ° C. If the specified value moves in the lower range (in the case of the examples listed below 40% by volume), the lower the value given here, the better the paraffin dispersing behavior. However, very high values in column 13 (in the case of the examples listed above 60% by volume) are also an indication of good paraffin dispersion behavior. Paraffin sedimentation is usually critical of about 10 to 30% by volume, since then most of the precipitated paraffin crystals are in the 20% by volume soil phase used to characterize the effectiveness of the additives as described.
Aus Tabelle 2 ist aus den Delta-CP-Werten (Spalte 10) ersichtlich, dass bei den Kraftstoffproben mit Biodiesel-Anteil in allen Fällen mit K1 eine eindeutige Verbesserung des Dispergierverhaltens im Vergleich zu K2 oder K3 erzielt wird. Die Versuche der Serien 8 und 9 in Tabelle 2 zeigen den überraschenden Effekt der erfindungsgemäßen Mischung auf die Paraffinsedimentation von Dieselkraftstoff-Biodiesel-Mischungen. In reinem Dieselkraftstoff (reiner Kraftstoff DK3) werden mit K1 und K2 etwa gleich gute Wirkungen erzielt, während K3 in neueren, schwefelarmen Dieselkraftstoffen keine ausreichende Performance mehr besitzt (Versuch 9-2). Durch Zugabe von 5 Gew.-% RME - wie z.B. in den Versuchen 8-3/4 und 9-4/6 - verschlechtert sich die Wirkung bei Verwendung der Vergleichsbeispiele K2 drastisch, während die Kälteeigenschaften bei Einsatz der erfindungsgemäßen Mischung nahezu unverändert bleiben.From Table 2 it can be seen from the delta CP values (column 10) that in the case of the fuel samples with biodiesel content, in all cases with K1 a clear improvement of the dispersing behavior is achieved in comparison to K2 or K3. The tests of series 8 and 9 in Table 2 show the surprising effect of the mixture according to the invention on the paraffin sedimentation of diesel fuel-biodiesel mixtures. In pure diesel fuel (pure fuel DK3) are about equally good with K1 and K2 K3 does not have sufficient performance in newer, low-sulfur diesel fuels (experiment 9-2). By adding 5 wt .-% RME - as in the experiments 8-3 / 4 and 9-4 / 6 - the effect deteriorates drastically with the use of Comparative Examples K2, while the cold properties remain virtually unchanged when using the mixture according to the invention.
Jedoch auch bei den Proben 9-1 bis 9-3 mit Mitteldestillat-Kraftstoff ohne Biodiesel-Zusatz (also einer Kraftstoffprobe rein auf Erdölbasis) ist eine leichte Verbesserung im Dispergierverhalten mit K1 gegenüber K2 und K3 zu beobachten, erkenntlich an dem geringeren Sediment-Wert bei annähernd gleichen CP- und CFPP-Werten.However, even with samples 9-1 to 9-3 with middle distillate fuel without biodiesel additive (ie a fuel sample purely based on petroleum), a slight improvement in the dispersion behavior with K1 compared to K2 and K3 can be observed, recognizable by the lower sediment value at approximately the same CP and CFPP values.
Claims (13)
- A mixture comprising(a) from 5 to 95% by weight of at least one polar oil-soluble nitrogen compound other than components (b) and (c) which is capable of sufficiently dispersing paraffin crystals precipitated out under cold conditions in fuels and is selected from reaction products formed from poly(C2- to C20-carboxylic acids) having at least one tertiary amino group with primary or secondary amines,(b) from 1 to 50% by weight of at least one oil-soluble acid amide formed from polyamines having from 2 to 1000 nitrogen atoms and C8- to C30-fatty acids and(c) from 0 to 50% by weight of at least one oil-soluble reaction product formed from α,β-dicarboxylic acids having 4 to 300 carbon atoms or derivatives thereof and primary alkylamines,the sum of all components of the mixture (a) to (c) adding up to 100% by weight.
- The mixture according to claim 1, comprising, as component (a), at least one oil-soluble reaction product based on poly(C2- to C20-carboxylic acids) which have at least one tertiary amino group and are of the general formula I or II
- The mixture according to claim 1 or 2, wherein the oil-soluble reaction product of component (a) is an amide, an amide ammonia salt or an ammonia salt, in which no, one or more carboxylic acid groups has/have been converted to amide groups.
- The mixture according to claims 1 to 3, wherein the parent amines of the oil-soluble reaction products of component (a) are secondary amines and have the general formula HNR2 in which the two variables R are each independently straight-chain or branched C10- to C30-alkyl radicals.
- The mixture according to claims 1 to 4, comprising, as component (b), at least one oil-soluble acid amide formed from aliphatic polyamines having from 2 to 6 nitrogen atoms and C16- to C20-fatty acids, all primary and secondary amino functions of the polyamines having been converted to acid amide functions.
- The use of the mixture according to claims 1 to 5 as an additive to fuels.
- The use of the mixture according to claim 6 as an additive to fuels which consist(A) to an extent of from 0.1 to 75% by weight of at least one biofuel oil which is based on fatty acid esters, and(B) to an extent of from 25 to 99.9% by weight of middle distillates of fossil origin and/or of vegetable and/or animal origin, which are essentially hydrocarbon mixtures and are free of fatty acid esters.
- The use according to claim 7, wherein fuel component (A) essentially comprises alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats.
- The use according to claims 6, 7 or 8 in the function as a paraffin dispersant.
- A fuel according to claims 6 to 8, comprising a mixture according to claims 1 to 5.
- The fuel according to claim 10, comprising, as further additives in amounts customary therefor, flow improvers, further paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
- A fuel additive concentrate comprising from 10 to 70% by weight, based on the total amount of the concentrate, of a mixture according to claims 1 to 5, dissolved in a hydrocarbon solvent.
- The fuel additive concentrate according to claim 12, comprising, as further additives in amounts customary therefor, flow improvers, further paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
Priority Applications (2)
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PL07730085T PL2038380T3 (en) | 2006-06-22 | 2007-06-12 | Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels |
EP07730085A EP2038380B1 (en) | 2006-06-22 | 2007-06-12 | Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels |
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EP06115866 | 2006-06-22 | ||
PCT/EP2007/055760 WO2007147753A2 (en) | 2006-06-22 | 2007-06-12 | Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels |
EP07730085A EP2038380B1 (en) | 2006-06-22 | 2007-06-12 | Mixture from polar oil-soluble nitrogen compounds and acid amides as paraffin dispersant for fuels |
Publications (2)
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EP2038380A2 EP2038380A2 (en) | 2009-03-25 |
EP2038380B1 true EP2038380B1 (en) | 2009-12-09 |
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US (1) | US8187345B2 (en) |
EP (1) | EP2038380B1 (en) |
JP (1) | JP2009541507A (en) |
KR (1) | KR101317613B1 (en) |
CN (1) | CN101473018B (en) |
AT (1) | ATE451441T1 (en) |
AU (1) | AU2007263066B2 (en) |
BR (1) | BRPI0713128A2 (en) |
CA (1) | CA2655877C (en) |
DE (1) | DE502007002278D1 (en) |
ES (1) | ES2336962T3 (en) |
MX (1) | MX2008015550A (en) |
NO (1) | NO20085157L (en) |
PL (1) | PL2038380T3 (en) |
WO (1) | WO2007147753A2 (en) |
Families Citing this family (25)
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US20100005706A1 (en) | 2008-07-11 | 2010-01-14 | Innospec Fuel Specialties, LLC | Fuel composition with enhanced low temperature properties |
GB0902009D0 (en) | 2009-02-09 | 2009-03-11 | Innospec Ltd | Improvements in fuels |
EP2230226B1 (en) * | 2009-03-18 | 2017-01-18 | Infineum International Limited | Additives for fuel oils |
RU2508394C2 (en) * | 2009-04-07 | 2014-02-27 | Басф Се | Mixture of polar oil-soluble nitrogen compounds and oil-soluble aliphatic compounds for lowering cloud point in middle-distillate fuels |
GB2486255A (en) * | 2010-12-09 | 2012-06-13 | Innospec Ltd | Improvements in or relating to additives for fuels and lubricants |
BR112013023254B1 (en) | 2011-03-11 | 2020-12-15 | Arkema Inc | PRE-MIXING POLYOL COMPOSITION AND METHOD TO STABILIZE A THERMOFIX FOAM MIXTURE |
CN103459566B (en) * | 2011-03-29 | 2015-01-28 | 日油株式会社 | Agent for improving fluidity of fuel oil and fuel oil composition |
US20150059238A1 (en) | 2012-04-27 | 2015-03-05 | Evonik Oil Additives Gmbh | Use of cold flow improver compositions for fuels, blends thereof with biofuels and formulations thereof |
RU2561279C1 (en) * | 2014-09-19 | 2015-08-27 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Paraffin dispersant, method for production thereof and fuel composition, content thereof |
CN104403706B (en) * | 2014-11-20 | 2016-06-22 | 中国石油大学(北京) | A kind of novel diesel wax crystal dispersing agent |
US10557096B2 (en) | 2014-11-27 | 2020-02-11 | Basf Se | Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels |
US11060044B2 (en) | 2016-05-24 | 2021-07-13 | Basf Se | Copolymer and use thereof for reducing crystallization of paraffin crystals in fuels |
CN106518788B (en) * | 2016-09-28 | 2019-04-02 | 中国石油化工股份有限公司 | Wax crystalline substance, asphaltene dispersants for High viscosity crude |
WO2018064270A1 (en) | 2016-09-29 | 2018-04-05 | Ecolab USA, Inc. | Paraffin inhibitors, and paraffin suppressant compositions and methods |
AU2017335819B2 (en) | 2016-09-29 | 2021-10-21 | Ecolab Usa Inc. | Paraffin suppressant compositions and methods |
WO2020115135A1 (en) | 2018-12-04 | 2020-06-11 | Total Marketing Services | Hydrogen sulphide and mercaptans scavenging compositions |
EP3891260A1 (en) | 2018-12-04 | 2021-10-13 | Total Marketing Services | Hydrogen sulphide and mercaptans scavenging compositions |
WO2020115133A1 (en) | 2018-12-04 | 2020-06-11 | Total Marketing Services | Hydrogen sulphide and mercaptans scavenging compositions |
EP3913035A1 (en) | 2020-05-20 | 2021-11-24 | Basf Se | Novel compositions for reducing crystallization of paraffin crystals in fuels |
SI4074810T1 (en) | 2021-04-15 | 2024-05-31 | Basf Se | New compositions for reducing crystallization of paraffin crystals in fuels |
WO2023025636A1 (en) | 2021-08-27 | 2023-03-02 | Basf Se | Aqueous dispersions of paraffin inhibitors |
WO2023057748A1 (en) | 2021-10-04 | 2023-04-13 | Innospec Fuel Specialties Llc | Improvements in fuels |
EP4166633A1 (en) | 2021-10-15 | 2023-04-19 | Innospec Fuel Specialties LLC | Improvements in fuels |
WO2024056479A1 (en) | 2022-09-12 | 2024-03-21 | Basf Se | New compositions for reducing crystallization of paraffin crystals in fuels |
WO2024115211A1 (en) | 2022-11-30 | 2024-06-06 | Basf Se | Homo- and copolymers of vinyl ethers for reducing crystallization of paraffin crystals in fuels |
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GB842991A (en) | 1956-11-02 | 1960-08-04 | Du Pont | Fuel oil compositions |
GB1410788A (en) | 1972-12-18 | 1975-10-22 | Basf Ag | Gasoline fuels for internal combustion engines |
DE2828038A1 (en) * | 1978-06-26 | 1980-01-10 | Basf Ag | FUELS FOR OTTO ENGINES |
DE3049553A1 (en) | 1980-12-31 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | PETROLEUM DISTILLATES WITH IMPROVED COLD BEHAVIOR |
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DE19848621A1 (en) | 1998-10-21 | 2000-04-27 | Basf Ag | Mixture useful as a wax antisettling and lubricity additive for middle distillates comprises reaction products of a tertiary amine polycarboxylic acid and a secondary amine and of maleic anhydride and a primary alkylamine |
GB0011733D0 (en) * | 2000-05-16 | 2000-07-05 | Infineum Int Ltd | Additives for improved engine operation |
DE10349851B4 (en) * | 2003-10-25 | 2008-06-19 | Clariant Produkte (Deutschland) Gmbh | Cold flow improver for fuel oils of vegetable or animal origin |
PL1801187T3 (en) * | 2005-12-22 | 2016-04-29 | Clariant Produkte Deutschland | Mineral oils containing detergent additives with improved cold flowability |
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2007
- 2007-06-12 BR BRPI0713128-3A patent/BRPI0713128A2/en not_active IP Right Cessation
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- 2007-06-12 AT AT07730085T patent/ATE451441T1/en active
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- 2007-06-12 AU AU2007263066A patent/AU2007263066B2/en not_active Ceased
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- 2007-06-12 KR KR1020097000680A patent/KR101317613B1/en active IP Right Grant
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JP2009541507A (en) | 2009-11-26 |
DE502007002278D1 (en) | 2010-01-21 |
WO2007147753A3 (en) | 2008-04-17 |
EP2038380A2 (en) | 2009-03-25 |
CA2655877A1 (en) | 2007-12-27 |
BRPI0713128A2 (en) | 2012-04-17 |
KR101317613B1 (en) | 2013-10-10 |
US20090188159A1 (en) | 2009-07-30 |
MX2008015550A (en) | 2008-12-17 |
PL2038380T3 (en) | 2010-05-31 |
AU2007263066B2 (en) | 2011-04-28 |
CN101473018B (en) | 2013-06-12 |
WO2007147753A2 (en) | 2007-12-27 |
KR20090026189A (en) | 2009-03-11 |
AU2007263066A1 (en) | 2007-12-27 |
CN101473018A (en) | 2009-07-01 |
ATE451441T1 (en) | 2009-12-15 |
CA2655877C (en) | 2015-08-04 |
US8187345B2 (en) | 2012-05-29 |
ES2336962T3 (en) | 2010-04-19 |
NO20085157L (en) | 2008-12-18 |
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