EP0078249B1 - Additive with a combustion promoting and soot inhibiting activity for furnace oils, diesel fuels and other liquid combustion and fuel substances, as well as the aforesaid liquid combustion and fuel substances - Google Patents
Additive with a combustion promoting and soot inhibiting activity for furnace oils, diesel fuels and other liquid combustion and fuel substances, as well as the aforesaid liquid combustion and fuel substances Download PDFInfo
- Publication number
- EP0078249B1 EP0078249B1 EP19820890134 EP82890134A EP0078249B1 EP 0078249 B1 EP0078249 B1 EP 0078249B1 EP 19820890134 EP19820890134 EP 19820890134 EP 82890134 A EP82890134 A EP 82890134A EP 0078249 B1 EP0078249 B1 EP 0078249B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- combustion
- fuels
- oil
- additive
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000002485 combustion reaction Methods 0.000 title claims description 39
- 239000000654 additive Substances 0.000 title claims description 38
- 230000000996 additive effect Effects 0.000 title claims description 27
- 239000000446 fuel Substances 0.000 title claims description 24
- 239000004071 soot Substances 0.000 title claims description 20
- 239000007788 liquid Substances 0.000 title claims description 11
- 230000002401 inhibitory effect Effects 0.000 title claims description 7
- 239000000295 fuel oil Substances 0.000 title claims description 4
- 239000002283 diesel fuel Substances 0.000 title description 18
- 239000000126 substance Substances 0.000 title description 4
- 230000001737 promoting effect Effects 0.000 title description 2
- 239000003112 inhibitor Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 48
- 238000010438 heat treatment Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 15
- 230000032683 aging Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- FQKUGOMFVDPBIZ-UHFFFAOYSA-N flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 low aromatics Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical class CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 150000003751 zinc 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
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- the invention relates to an additive with a combustion-promoting and soot-inhibiting effect on heating oils, diesel fuels and other liquid fuels, in particular with a boiling end at normal pressure above 300 ° C., the addition one or more oil-soluble and / or oil-dispersible compounds of transition metals such as combustion-catalytically active Contains iron, manganese, molybdenum, cobalt, nickel or copper, and / or alkaline earths, and one or more inhibitors against polymerization and oxidation of hydrocarbons.
- the invention further relates to liquid fuels with such an additive.
- soot deposits which due to their large surface area also adsorb acidic components, especially sulfuric acid, also cause increased corrosion and thus material losses in the exhaust system of such systems.
- the oil When burning heating oils and diesel fuels, the oil is usually sprayed into the combustion zone in the form of droplets that are as finely divided as possible (except for small gasification burners).
- the individual droplets are quickly heated up in this hot zone and at least partially evaporated.
- these vaporized hydrocarbons mix with the atmospheric oxygen and maintain the flame formation, whereby the corresponding combustion products are formed.
- As these droplets move through the combustion zone their size continuously decreases until the volatile components have evaporated (and burned).
- a small or large remnant of non-volatile constituents remains, which consist of highly polymeric organic compounds, carbon and impurities.
- hydrocarbons When hydrocarbons are heated to a high degree, they crack, whereby larger molecules are broken down into smaller ones.
- organometallic, organic and inorganic compounds can serve as combustion-promoting additives.
- organometallic compounds have proven to be favorable as combustion catalysts of hydrocarbons in certain cases, since on the one hand they can be finely divided into solution / dispersion in oil-soluble / oil-dispersible form and on the other hand compounds of transition and / or alkaline earth metals have shown good effects as combustion catalysts.
- heating oils and diesel fuels from petroleum or synthetic oils
- stabilization thereof during storage is to ensure that the application properties of these hydrocarbons do not deteriorate over time through oxidation and polymerization.
- inhibitors can be added, which are widely used in practice especially in the case of carburetor fuels and lubricating oils, but can also be used in heating oils and diesel fuels, see below.
- MMT methylcyclopentadienylmanganese tricarbonyl
- ferrocene dicyclopentadienyl iron
- a well-known short method for determining the stability of middle distillates is the accelerated stability test (also EDM diesel test, Union Pacific or Nalco and Du Pont test) at 149 ° C (300 ° Fahrenheit).
- This test determines the relative stability of middle distillates under short-term aging conditions at high temperature and with access to air. The procedure consists in aging the distillate sample at 149 ° C (300 ° Fahrenheit) for 90 minutes with the entry of air and filtering off the residues formed.
- the filter covering is rated with numbers from 1-20 and provides a comparison of the aging stability of the distillates tested. The lower the rating number, the more stable the distillate, whereby a number up to a maximum of 7 is usually considered to be satisfactory.
- the color of the distillate is determined according to ASTM (D - 1500 - 58 T) before and after aging, which also allows a relative evaluation of the stability.
- Polymerization and oxidation inhibitors are known per se and are used in a wide variety of products such as e.g. B. food, cosmetics, plastics, rubber and also used in mineral oil derivatives. It has been shown that these inhibitors are largely ineffective in the products for combustion promotion at issue here. For mineral oil distillates and residual oils, specific inhibitors have also been used to improve storage stability. All of these known oxidation and polymerization inhibitors have hitherto been used to stabilize the products at conventional storage temperatures. A temperature stress of these heating oil and diesel fuel inhibitors of over 150 ° C. has not been provided.
- the object of the invention is to provide an additive for heating oils and diesel fuels and other liquid fuels, which hinders the polymerization at temperatures of in particular 300 ° C. and above.
- there is a sharp increase in the reaction rate at temperatures above 300 ° C. the tendency of unsaturated hydrocarbons to polymerize being significantly further favored by the presence of metal compounds, in particular the transition group. It is therefore of particular interest to hinder precisely these high-temperature reactions, since they lead to the increased formation of unburned carbon and high-molecular tarry hydrocarbon compounds (which usually also contain polycyclic aromatics), which can have cancerogenic properties.
- the inhibitors used for this purpose must neither decompose nor evaporate at this temperature at normal pressure (boiling point or sublimation above 300 ° C).
- the antioxidants and antipolymerizers which are already known for the stabilization of heating oils and distillates cannot be used for the present purposes since they do not meet these conditions.
- BHT 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylp-cresol
- BHA sterically hindered xylenols and trimethylphenols
- BHA butylated hydroxyanisoles
- TBHQ middle distillates
- para-cresols and aromatic amines are used.
- These inhibitors are only suitable for temperature ranges up to about 150 ° C.
- Oxidation and polymerization inhibitors which are also intended for higher temperature loads, have already been used to stabilize plastics, lubricating oils and asphalts.
- An anti-aging agent known for heat resistant rubber articles is e.g. the zinc salt of 2-mercapto-benzimidazole. However, this inhibitor is also decomposed at temperatures of 300 ° C and is not suitable for higher temperatures.
- US Pat. No. 2,697,033 is known to include Zn-dicyclohexyldithiophosphate and Ca-petroleum sulfonate in oils to stabilize the storage.
- the thermal-oxidative decomposition behavior of the Zn-dicyclohexyldithiophosphate is so unfavorable that the inhibitor function is not fulfilled.
- the start of decomposition is at normal pressure, at 10 6 Pa and at 5 x 10 6 Pa far below 300 ° C.
- A1kylphenole which serve oil-soluble for the preparation of alkaline earth metal salts.
- these must be reactive phenols, preferably monoalkylphenols, which are consequently unsuitable as oxidation and polymerization inhibitors.
- octyl- to dodecylphenols have a vapor pressure of the order of 101,000 Pa, which means that they evaporate completely or to a considerable extent at this temperature and are therefore unsuitable for polymerization-inhibiting catalysis at this temperature.
- GB-A-800445 shows the use of Mg naphthenate and refractory oxides such as e.g. B. silicon oxide.
- Mg naphthenate and refractory oxides such as e.g. B. silicon oxide.
- refractory oxides such as e.g. B. silicon oxide.
- such mixtures have disadvantages and are not suitable for producing the desired effect.
- the addition with combustion-promoting and soot-inhibiting effect to heating oils, diesel fuels and other liquid fuels is characterized in that the combustion-catalytically active oil-soluble and / or oil-dispersible compounds of alkaline earths are those of calcium, strontium and / or barium and that as Inhibitor is an oxidation and polymerization inhibitor based on sterically hindered heat-stable alkylphenols with an average molecular weight of 280 or based on N-phenylnaphtylamine (molecular weight 219), the inhibitor having a heat resistance so that it due to its vapor pressure and / or its decomposition temperature temperatures of 300 ° C and above can be exposed at least briefly at normal pressure without losing its polymerization-inhibiting effect.
- the weight ratio metal: inhibitor 1: 0.1 to 10.
- Liquid fuels according to the invention in particular those with a boiling end at normal pressure above 300 ° C., such as heating oils and diesel fuels, are characterized in that they contain the additive described above.
- the metal content in the liquid fuel and propellant can be 0.1 to 1000 Ge parts by weight per million parts by weight of the fuels mentioned.
- the addition according to the invention on the one hand improves the shelf life of the fuels mentioned and on the other hand also effectively inhibits the polymerizations described above, which are accelerated enormously at temperatures of over 300 ° C. At the same time, the advantage of more complete combustion is achieved even with less excess air. This is all the more important since the aforementioned trend towards using heavier cuts and products from conversion plants, in particular catalytic and thermal crackers and coking plants, in heating oils and diesel fuels is constantly increasing.
- the polymerization inhibitors used according to the present invention are also effective at temperatures above 300 ° C. They are not only thermally stable under the effects of heat for as long as the hydrocarbon droplet to be burned passes through the combustion zone, but they also advantageously provide effective protection against oxidation for heating oils and diesel fuels at the normal normal storage temperatures.
- Such inhibitors are high boiling phenols with longer chain, sterically hindering alkyl groups such as e.g. Nonyle.
- the higher molecular weight organic amine compound N-phenyl-2-naphthylamine also fulfills the present condition. In practice, of course, any carcinogenic effects must always be observed and the harmful additives must be preferred, although heating oils and diesel fuels should normally not come into contact with the skin or with food.
- Inhibitors based on highly alkylated or polymeric sterically hindered phenol compounds have proven to be particularly economical and advantageously do not result in any increases in pollutants by SO 2 / SO 3 or nitrogen oxides, phosphorus compounds etc. in the exhaust gas.
- the soot number according to Bacharach was 3 with an air number of 1.4.
- a soot number of 3.3 was measured for the Unitherm burner with the same air ratio.
- the boiler efficiency, measured with the heat quantity measuring device, was 76.0-76.3% and 75.8-76.2% for the burners mentioned.
- the soot number for the Olymp burner improved to 1.5 for the same air ratio (1.4) and even to 1.2 for the Unitherm burner.
- the boiler efficiency of the additive heating oil was found to be 79.5-80.0% (Olymp burner) and 82.0-83.0% (Unitherm burner) when using the same heat measuring device.
- the average gain in efficiency was 3.6 and 6.5% due to the additives.
- composition of the additive according to the invention was:
- Extra-light, light heating oil with the following analysis data is, with and without addition, according to the invention in a Vossmann, Duo Parola-E, steel boiler with a Weiswash oil burner type WL 2/3 with a heat output of max. 81 kW burned.
- the soot number at 12.3-12.4% CO 2 and 16.4% CO 2 + 0 2 was reduced under analogous combustion conditions 0.01% CO in the exhaust gas reduced to an average of 1.06, ie improved by 2 points.
- This gas oil complies with the European regulations for use as diesel fuel.
- the following additives according to the invention were added to the gas oil, alkylated phenol according to Examples 1 and 2, sterically hindered tertnonyl-cresols, N-phenyl-2-naphthylamine and other highly evaporative polymerization and oxidation inhibitors with a boiling point (boiling range) of over 300 ° C. at normal pressure were included.
- the finished additive was added with 1 part by weight of additive to 2000 parts by weight of gas oil.
- the following improvements in the carbon black number were achieved for the following metal contents in the additive according to the invention:
- This coker gas oil (without additive) was subjected to the accelerated aging text described above at 149 ° C (300 ° Fahrenheit) for 90 minutes.
- the color number was 9.
- the color number became 14 with the same accelerated aging, to 16 in the presence of 15 ppm manganese (from MMT) and in 15 ppm copper (from copper naphtenate) increased to 18.
- the non-additive coker gas oil described in Example 4 was used in trucks as diesel fuel. Practical operation of these motor vehicles was not possible with the product, however, as these diesel engines showed very strong and unreasonable smoke emissions not only at full load, but also during normal operation, which may be due to the high content of aromatics and unsaturated hydrocarbons.
- An additive according to the invention consisting of 15% by weight of MMT, 20% by weight of alkylated phenols according to Examples 1 and 2 and 65% by weight of paraffin-based petroleum, was used in a ratio of 1 part by weight of additive to 700 parts by weight of coker gas oil admitted.
- the manganese content was 52.8 ppm, that of high-boiling alkylated phenols 28.6 ppm in the coker gas oil.
- the smoke development of the diesel engines operated with it was drastically reduced and averaged 20 Hartridge units.
- the residues in the combustion cylinders of the engines operated with it were negligible even after several months of use and the injection in excellent condition.
- Residual heating oils containing heavy parts from visbreakers had the following analysis data:
- This heavy residual oil was treated with 100 ppm manganese (from manganese naphtenate) and silicon dioxide obtained by flame hydrolysis of silicon tetrachloride with a BET surface area of approx. 200 (Aerosil 200) in an amount of 50 ppm plus aluminum oxide with a BET surface area of approx. 100 ( Aluminum oxide-C) also added in an amount of 50 ppm.
- silanol groups on the surface of the highly disperse silica as well as analogous aluminum hydroxides in the highly disperse aluminum oxide are likely to be responsible for the polymerization inhibition at temperatures above 300 ° C, while the manganese may have catalytically favored the combustion of carbon or carbon-enriched particles in the colder zone of the combustion . It shows that the inorganic polymerization inhibitors according to the invention can also be used advantageously for the present purposes.
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Description
Die Erfindung betrifft einen Zusatz mit verbrennungsfördernder und russhemmender Wirkung zu Heizölen, Dieselkraftstoffen und sonstigen flüssigen Brenn- und Treibstoffen, insbesondere mit Siedeende bei Normaldruck von über 300 °C, wobei der Zusatz ein oder mehrere verbrennungskatalytisch wirksame öllösliche und/oder öldispergierbare Verbindungen von Übergangsmetallen wie Eisen, Mangan, Molybdän, Kobalt, Nickel oder Kupfer, und/oder Erdalkalien, und ein oder mehrere Inhibitoren gegen Polymerisation und Oxidation von Kohlenwasserstoffen enthält. Weiters betrifft die Erfindung flüssige Brenn- und Treibstoffe mit einem solchen Zusatz.The invention relates to an additive with a combustion-promoting and soot-inhibiting effect on heating oils, diesel fuels and other liquid fuels, in particular with a boiling end at normal pressure above 300 ° C., the addition one or more oil-soluble and / or oil-dispersible compounds of transition metals such as combustion-catalytically active Contains iron, manganese, molybdenum, cobalt, nickel or copper, and / or alkaline earths, and one or more inhibitors against polymerization and oxidation of hydrocarbons. The invention further relates to liquid fuels with such an additive.
Durch die Erhöhung der Rohölpreise in den Jahren seit 1973 wurde die bestmögliche Verbrennung und Ausnützung des Wärmeinhaltes von Heizölen und Dieselkraftstoffen zu einer wirtschaftlichen Notwendigkeit. Auch der Umweltschutz ist ein immer wichtigeres Anliegen der Bevölkerung geworden. Die Vermeidung von Russ- und Rauchbildung bei Verbrennungsvorgängen mit geringstmöglichem Luftüberschuss kommt beiden vorgenannten Forderungen entgegen, nämlich Erhöhung der Wirtschaftlichkeit sowie Vermeidung von Umweltschäden und Belästigungen.The increase in crude oil prices in the years since 1973 made the best possible combustion and utilization of the heat content of heating oils and diesel fuels an economic necessity. Environmental protection has also become an increasingly important concern of the population. The avoidance of soot and smoke formation during combustion processes with the least possible excess of air meets both of the above requirements, namely increasing economic efficiency and avoiding environmental damage and nuisance.
Es ist bekannt, dass der Luftüberschuss einer der wesentlichsten Faktoren ist, welcher den Wärmewirkungsgrad einer Verbrennungsanlage beeinflusst. Je mehr überschüssige Luft unnötig aufgeheizt wird, desto grösser sind die Abwärmeverluste. Durch die Minimierung des Luftüberschusses werden die Verluste an nutzbarer Wärme verringert, wobei jedoch gleichzeitig die Tendenz zur erhöhten Russbildung verstärkt wird. Diese Bildung von unvollständig verbrannten, kohlenstoffangereicherten festen Partikeln beeinträchtigt den Wärmeübergang auf den Übertragungsflächen sowie die Dynamik des Abgassystems.It is known that excess air is one of the most important factors influencing the thermal efficiency of an incinerator. The more excess air is unnecessarily heated, the greater the waste heat losses. By minimizing the excess air, the losses of usable heat are reduced, but at the same time the tendency towards increased soot formation is increased. This formation of incompletely burned, carbon-enriched solid particles affects the heat transfer on the transfer surfaces and the dynamics of the exhaust system.
Die Russablagerungen, welche infolge ihrer grossen Oberfläche auch saure Anteile, insbesondere Schwefelsäure adsorbieren, bewirken auch erhöhte Korrosionen und damit Materialverluste im Abgassystem solcher Anlagen.The soot deposits, which due to their large surface area also adsorb acidic components, especially sulfuric acid, also cause increased corrosion and thus material losses in the exhaust system of such systems.
Die Verschlechterung der Wärmeausbeute bei Russbildung nimmt mit der Zeit zu, da sich die Belagsbildung, Korrosion etc. laufend verstärkt. Bei einer Untersuchung von über 100 000 Brennereinheiten in einer Grossstadt hat sich gezeigt, dass die Abnahme des Betriebswirkungsgrades während einer Heizperiode durchschnittlich 10 Relativprozent betrug. Laufende Reinigungen solcher Heizanlagen wären daher notwendig, was jedoch nicht nur kostenaufwendig ist, sondern auch nicht immer zum erwünschten Erfolg führt. Durch Abnutzung der Brenner und auch durch Witterungseinflüsse (Sturm, Niederdruckperioden etc.) kann die Russbildung durch unvollständige Verbrennung sehr bald auch nach erfolgter Reinigung wieder einsetzen. Es wurde daher besonders in den letzten Jahren intensiv untersucht, welche Möglichkeiten bestehen, um durch chemische Zusätze eine vollständigere Verbrennung ohne unnötigen Luftüberschuss zu erzielen.The deterioration of the heat yield during soot formation increases over time, as the formation of deposits, corrosion, etc. is constantly increasing. A study of over 100,000 burner units in a large city has shown that the decrease in operating efficiency during an heating period averaged 10 relative percent. Ongoing cleaning of such heating systems would therefore be necessary, which is not only expensive, but also does not always lead to the desired success. Wear of the burners and weather conditions (storms, low-pressure periods, etc.) can cause soot formation to resume very quickly even after cleaning, due to incomplete combustion. It has therefore been intensively investigated, particularly in recent years, what possibilities exist to achieve a more complete combustion without unnecessary excess air using chemical additives.
Bei der Verbrennung von Heizölen und Dieselkraftstoffen wird üblicherweise (ausser bei kleinen Vergaserbrennern) das Öl in Form von möglichst fein verteilten Tröpfchen in die Verbrennungszone eingesprüht. Die einzelnen Tröpfchen werden in dieser heissen Zone rasch aufgeheizt und zumindest teilweise verdampft. Rund um die Tröpfchen mischen sich diese verdampften Kohlenwasserstoffe mit dem Luftsauerstoff und erhalten die Flammenbildung, wobei sich die entsprechenden Verbrennungsprodukte bilden. Während diese Tröpfchen die Verbrennungszone durchwandern, verringert sich laufend ihre Grösse bis die flüchtigen Bestandteile verdampft (und verbrannt) sind. Je nach der Zusammensetzung der einzelnen Brenn- und Treibstoffe verbleibt ein kleiner oder grösserer Rest an nichtflüchtigen Bestandteilen, welche aus hochpolymeren organischen Verbindungen, Kohlenstoff und Verunreinigungen bestehen. Bei der starken Erhitzung von Kohlenwasserstoffen tritt Krackung derselben ein, wobei grössere Moleküle in kleinere aufgespaltet werden. Hiebei bilden sich leichtere Kohlenwasserstoffe, Wasserstoff etc. sowie reaktionsfreudige ungesättigte Verbindungen, welche weiter polymerisieren können. Diese teerigen Rückstände bis zu Kohlenstoff selbst verbrennen im Gegensatz zu Wasserstoff und den leichten Kohlenwasserstoffen wesentlich schwerer und oft auch unvollständig. Infolge der langsameren Oxydation dieser Rückstände durch den Luftsauerstoff genügt die Zeitspanne in der heissen Verbrennungszone nicht zur vollständigen, rückstandsfreien Verbrennung.When burning heating oils and diesel fuels, the oil is usually sprayed into the combustion zone in the form of droplets that are as finely divided as possible (except for small gasification burners). The individual droplets are quickly heated up in this hot zone and at least partially evaporated. Around the droplets, these vaporized hydrocarbons mix with the atmospheric oxygen and maintain the flame formation, whereby the corresponding combustion products are formed. As these droplets move through the combustion zone, their size continuously decreases until the volatile components have evaporated (and burned). Depending on the composition of the individual fuels, a small or large remnant of non-volatile constituents remains, which consist of highly polymeric organic compounds, carbon and impurities. When hydrocarbons are heated to a high degree, they crack, whereby larger molecules are broken down into smaller ones. Lighter hydrocarbons, hydrogen etc., as well as reactive unsaturated compounds, which can polymerize further, are formed here. In contrast to hydrogen and light hydrocarbons, these tarry residues up to carbon burn much more heavily and often incompletely. As a result of the slower oxidation of these residues by atmospheric oxygen, the period in the hot combustion zone is not sufficient for complete, residue-free combustion.
Der Ablauf des Verbrennungsvorganges wird durch den maskierenden Effekt, welchen der Ölnebel auf die Wärmeübertragung ausübt sowie durch die Verringerung des Sauerstoffgehaltes in der unmittelbaren Umgebung der verbrennenden Öltröpfchen noch weiter verzögert. Während der Zeitspanne, in welcher die Aufheizung der Öltröpfchen und Verdampfung der leichten Anteile stattfindet, wird die Polymerisation und Pyrolyse in dem verbliebenen Ölanteil entsprechend gefördert.The course of the combustion process is further delayed by the masking effect which the oil mist has on the heat transfer and by the reduction in the oxygen content in the immediate vicinity of the burning oil droplets. During the period in which the heating of the oil droplets and evaporation of the light components takes place, the polymerization and pyrolysis in the remaining oil component is promoted accordingly.
Der Ablauf oben beschriebener chemischer Reaktionen wird bei Temperaturen von über 300 °C stark beschleunigt, so dass daher die Brennstoffanteile mit darüberliegendem Siedebereich solch einer Polymerisation während der Verbrennung stärker ausgesetzt sind. Sowohl aus wirtschaftlichen Gründen als auch aus Gründen der Verfügbarkeit werden auch extraleichte Heizöle und Dieselkraftstoffe bei der Herstellung so geschnitten, dass die über 300 °C bei Normaldruck siedenden Anteile immer grösser werden. Wenn man früher bei den vorgenannten Produkten je nach saisonaler Qualität ein Siedeende von 320/350 °C vorsah, liegt dieses derzeit häufig bereits bei 380°C. Durch die sprunghafte Entwicklung beim Bau und Einsatz von Konversionsanlagen zur Umwandlung von Rückständen in leichtere Produkte steigt der Anteil der ungesättigten und damit auch thermisch unstabileren Moleküle in den marktüblichen Mitteldestillaten weiter an. Diese verstärkt zur Polymerisation neigenden Anteile bilden daher auch eine Quelle höherer Russbildung.The course of the chemical reactions described above is greatly accelerated at temperatures above 300 ° C., so that the fuel components with a boiling range above are more exposed to such polymerization during combustion. For economic reasons as well as for reasons of availability, extra-light heating oils and diesel fuels are cut in the production process in such a way that the parts boiling above 300 ° C at normal pressure become ever larger. If, in the past, a boiling end of 320/350 ° C was provided for the aforementioned products depending on the seasonal quality, this is often already at 380 ° C at the moment. Due to the rapid development in the construction and use of conversion systems for converting residues into lighter products, the proportion of unsaturated and therewith also increases Mix more unstable molecules in the middle distillates customary on the market. These components, which tend to polymerize, therefore also form a source of higher soot formation.
Beide Tendenzen, nämlich höheres Siedeende und mehr ungesättigte Anteile, welche sich in den nächsten Jahren noch weiter verstärken werden, erschweren die vollständige Verbrennung bei möglichst nahstöchiometrischen Luftmengen. Um hier Abhilfe zu schaffen, werden seit längerer Zeit chemische Zusätze ge- und untersucht, um die Verbrennung von Heizölen und Dieselkraftstoffen katalytisch zu begünstigen, d.h. eine vollständige Verbrennung in einer möglichst kurzen Zeitspanne bzw. bei niedrigeren Temperaturen zu erreichen.Both tendencies, namely a higher boiling point and more unsaturated components, which will increase further in the next few years, complicate the complete combustion with the air volumes that are as close as possible to stoichiometric. To remedy this situation, chemical additives have been investigated and investigated for a long time in order to catalytically favor the combustion of heating oils and diesel fuels, i.e. to achieve complete combustion in the shortest possible time or at lower temperatures.
Es ist bekannt, dass als verbrennungsfördernde Zusätze metallorganische, organische und anorganische Verbindungen dienen können. So haben sich metallorganische Verbindungen als Verbrennungskatalysatoren von Kohlenwasserstoffen in bestimmten Fällen als günstig erwiesen, da diese einerseits in öllöslicher/öldispergierbarer Form feinstverteilt in Lösung/Dispersion gebracht werden können und andererseits Verbindungen der Übergangs- und/oder Erdalkalimetalle gute Wirkungen als Verbrennungskatalysatoren gezeigt haben.It is known that organometallic, organic and inorganic compounds can serve as combustion-promoting additives. Thus, organometallic compounds have proven to be favorable as combustion catalysts of hydrocarbons in certain cases, since on the one hand they can be finely divided into solution / dispersion in oil-soluble / oil-dispersible form and on the other hand compounds of transition and / or alkaline earth metals have shown good effects as combustion catalysts.
Eine Hypothese der Wirkung von Erdalkalien (Calzium, Strontium, Barium) und wahrscheinlich auch von Molybdän als Verbrennungsförderer ist die Gasphasekatalyse zur Aufspaltung von Wasserstoff- und Wassermolekülen auf Wasserstoffatome. Letztere reagieren rasch mit dem vorhandenen Wasserdampf unter Bildung von Hydroxyd-Radikalen, welche mit dem Kohlenstoff des Russes reagieren. Die Übergangsmetalle hingegen dürften als Metalloxyde wirksam werden und die Bildung von CO und C02 aus Kohlenstoff in der bereits wieder kühleren Zone der Verbrennung, wo auch ein höheres Sauerstoffanbot vorliegt, beschleunigen. Es ist bekannt und messbar, dass die Verbrennung von Kohlenstoff (Russ) bei niedrigeren Temperaturen stattfinden kann, wenn Katalysatoren der Übergangsmetalle in geeigneter Form anwesend sind. Die gleichzeitige Verwendung von Erdalkali- und Übergangsmetallen hat sich bei der Verbrennung als vorteilhaft erwiesen, da die beiden Gruppen nacheinander in der heisseren Zone sowie anschliessend bereits wieder kälteren, aber sauerstoffreicheren ihre katalytische Wirkung entfalten können.Gas phase catalysis to split hydrogen and water molecules onto hydrogen atoms is a hypothesis of the effect of alkaline earths (calcium, strontium, barium) and probably also of molybdenum as a combustion promoter. The latter react quickly with the existing water vapor to form hydroxide radicals, which react with the carbon of the soot. The transition metals, on the other hand, should act as metal oxides and accelerate the formation of CO and CO 2 from carbon in the already cooler zone of the combustion, where there is also a greater supply of oxygen. It is known and measurable that the combustion of carbon (soot) can take place at lower temperatures if catalysts of the transition metals are present in a suitable form. The simultaneous use of alkaline earth and transition metals has proven to be advantageous in the combustion, since the two groups can develop their catalytic effect one after the other in the hotter zone and then again colder but more oxygen-rich.
Der Zusatz von rein organischen Verbindungen (ohne Metallgehalt) wurde ebenfalls seit langem untersucht, hat jedoch bei Zugabe in den üblichen kleinen Additivmengen keine wesentliche verbrennungsfördernde Wirkung gebracht. So wurden Alkohole, Phenole, Ester, niedrige Aromaten, Hydrazinderivate, organische Amine, Naphten-und Carbonsäuren ohne Änderung der Verbrennung bzw. Beeinflussung der Rauchbildung getestet.The addition of purely organic compounds (without metal content) has also been studied for a long time, but when added in the usual small amounts of additives has not brought about any significant combustion-promoting effects. So alcohols, phenols, esters, low aromatics, hydrazine derivatives, organic amines, naphthenic and carboxylic acids were tested without changing the combustion or influencing the smoke formation.
Ein weiteres Problem beim Einsatz von Heizölen und Dieselkraftstoffen (aus Erd- oder Syntheseölen) stellt die Stabilisierung derselben bei der Lagerung dar. Es soll hiebei erreicht werden, dass sich die Anwendungseigenschaften dieser Kohlenwasserstoffe im Laufe der Zeit nicht durch Oxydation und Polymerisation verschlechtern. Zu diesem Zwecke können Inhibitoren zugesetzt werden, welche vor allem bei Vergaserkraftstoffen und Schmierölen in der Praxis breite Anwendung finden, jedoch auch bei Heizölen und Dieselkraftstoffen eingesetzt werden können, siehe dazu weiter unten.Another problem with the use of heating oils and diesel fuels (from petroleum or synthetic oils) is the stabilization thereof during storage. The aim is to ensure that the application properties of these hydrocarbons do not deteriorate over time through oxidation and polymerization. For this purpose, inhibitors can be added, which are widely used in practice especially in the case of carburetor fuels and lubricating oils, but can also be used in heating oils and diesel fuels, see below.
Ein besonderes Lagerproblem ergibt sich bei Produkten, welche metallorganische Verbindungen der Übergangsmetalle enthalten, wie insbesondere Kupfer-, Mangan-, Kobalt-, Nickel- und Eisenverbindungen, da diese die Alterung besonders bei ungesättigten Kohlenwasserstoffen beschleunigen. Es hat sich auch gezeigt, dass eine Alterungsverschlechterung sogar bei Anwesenheit dieser Metalle in Komplexform eintreten kann, wie z. B. bei Additivierung von Mitteldestillaten und schweren Heizölen mit Methylcyclopentadienylmangantricarbonyl (abgekürzt MMT) oder Dicyclopentadienyleisen (Ferrocen). Eine bekannte Kurzmethode zur Bestimmung der Stabilität von Mitteldestillaten stellt der beschleunigte Stabilitätstest (auch EDM-Dieseltest, Union Pacific oder Nalco sowie Du Pont Test) bei 149°C (300° Fahrenheit) dar. Dieser Test bestimmt die relative Stabilität von Mitteldestillaten unter kurzzeitigen Alterungsbedingungen bei hoher Temperatur und Lufzutritt. Das Verfahren besteht darin, dass die Destillatprobe bei 149°C (300° Fahrenheit) 90 Minuten lang unter Luftzutritt gealtert wird und die gebildeten Rückstände abfiltriert werden. Der Filterbelag wird je nach Stärke und Farbe mit Zahlen von 1-20 bewertet und ergibt einen Vergleich der Alterungsstabilität der getesteten Destillate. Je niedriger die Bewertungszahl, desto stabiler ist das Destillat, wobei meist eine Zahl bis zu maximal 7 als noch befriedigend angesehen wird. Zusätzlich zu der Filterbewertung wird auch noch die Farbe des Destillates nach ASTM (D - 1500 - 58 T) vor und nach der Alterung bestimmt, welche ebenfalls eine relative Bewertung der Stabilität zulässt.A particular storage problem arises in products which contain organometallic compounds of the transition metals, such as, in particular, copper, manganese, cobalt, nickel and iron compounds, since these accelerate aging particularly in the case of unsaturated hydrocarbons. It has also been shown that deterioration in aging can occur even in the presence of these metals in complex form, e.g. B. with additives of middle distillates and heavy heating oils with methylcyclopentadienylmanganese tricarbonyl (abbreviated MMT) or dicyclopentadienyl iron (ferrocene). A well-known short method for determining the stability of middle distillates is the accelerated stability test (also EDM diesel test, Union Pacific or Nalco and Du Pont test) at 149 ° C (300 ° Fahrenheit). This test determines the relative stability of middle distillates under short-term aging conditions at high temperature and with access to air. The procedure consists in aging the distillate sample at 149 ° C (300 ° Fahrenheit) for 90 minutes with the entry of air and filtering off the residues formed. Depending on the thickness and color, the filter covering is rated with numbers from 1-20 and provides a comparison of the aging stability of the distillates tested. The lower the rating number, the more stable the distillate, whereby a number up to a maximum of 7 is usually considered to be satisfactory. In addition to the filter evaluation, the color of the distillate is determined according to ASTM (D - 1500 - 58 T) before and after aging, which also allows a relative evaluation of the stability.
Die Anwendung dieses Tests zeigte wesentliche Erhöhungen der Bewertungszahlen nach der Alterung, wenn Kupfer-, Mangan-, Kobalt-, Nickel-und Eisenverbindungen (wie z.B. Naphtenate, Octoate, Sulfonate, aber auch Komplexverbindungen) den Mitteldestillaten zugesetzt wurden. Es ergaben sich Erhöhungen um mehrere Punkte - je nach der Zusammensetzung des Mitteldestillates - bei einem Gehalt an obigen Metallen von 10-25 Teile per Million Teile Kohlenwasserstoff (ppm).Use of this test showed significant increases in the rating numbers after aging when copper, manganese, cobalt, nickel and iron compounds (such as naphthenates, octoates, sulfonates, but also complex compounds) were added to the middle distillates. There were increases of several points - depending on the composition of the middle distillate - with a content of the above metals of 10-25 parts per million parts of hydrocarbon (ppm).
In der Praxis werden bei der Rückführung von überschüssigem Heizöl vom Brenner in den Tank diese Heizstoffe einer höheren als üblichen Lagertemperatur ausgesetzt, was die Polymerisations- und Oxidationsneigung weiter erhöht und oft stark beschleunigt und somit eine Qualitätsverschlechterung der Heizöle bewirkt.In practice, when excess fuel oil is returned from the burner to the tank, these fuels are exposed to a higher than usual storage temperature, which further increases and often accelerates the tendency to polymerize and oxidize, which in turn leads to a deterioration in the quality of the heating oils.
Es zeigt sich daher, dass nach bisherigem Stand der Technik die Verbrennung durch katalytisch wirkende öllösliche und/oder öldispergierbare Metallverbindungen wohl verbessert werden kann, dies aber gleichzeitig mit dem Nachteil einer erhöhten Alterung der damit behandelten Heizöle und Dieselkraftstoffe verbunden ist. Es wird dadurch in vielen Fällen der wirtschaftliche Vorteil der Verbrennungsförderung wieder zunichte gemacht und in noch grössere Nachteile, wie Brenner- und Leitungsverlegungen umgewandelt.It can therefore be seen that, according to the prior art, the combustion can be improved by catalytically active oil-soluble and / or oil-dispersible metal compounds can, but this is at the same time associated with the disadvantage of increased aging of the heating oils and diesel fuels treated with it. In many cases, the economic advantage of promoting combustion is thereby nullified and converted into even greater disadvantages, such as burner and line laying.
Polymerisations- und Oxydationsinhibitoren sind per se bekannt und werden bei einer breiten Anzahl von Produkten, wie z. B. Nahrungsmittel, Kosmetika, Kunststoffen, Kautschuk und auch bei Mineralölderivaten verwendet. Es hat sich gezeigt, dass diese Inhibitoren bei den hier zur Debatte stehenden Produkten zur Verbrennungsförderung weitgehend unwirksam sind. Bei Mineral- öldestillaten und Rückstandsölen wurden auch spezifisch dafür bestimmte Inhibitoren verwendet, um die Lagerstabilität zu verbessern. Alle diese bekannten Oxydations- und Polymerisations-Inhibitoren wurden bisher zur Stabilisierung der Produkte bei üblichen Lagertemperaturen eingesetzt. Eine Temperaturbeanspruchung dieser Heizöl-und Dieselkraftstoff-Inhibitoren von über 150°C ist dabei nicht vorgesehen worden.Polymerization and oxidation inhibitors are known per se and are used in a wide variety of products such as e.g. B. food, cosmetics, plastics, rubber and also used in mineral oil derivatives. It has been shown that these inhibitors are largely ineffective in the products for combustion promotion at issue here. For mineral oil distillates and residual oils, specific inhibitors have also been used to improve storage stability. All of these known oxidation and polymerization inhibitors have hitherto been used to stabilize the products at conventional storage temperatures. A temperature stress of these heating oil and diesel fuel inhibitors of over 150 ° C. has not been provided.
Aufgabe der Erfindung ist es, einen Zusatz für Heizöle und Dieselkraftstoffe und sonstige flüssige Brenn- und Treibstoffe vorzusehen, welcher die Polymerisation bei Temperaturen von insbesondere 300°C und darüber behindert. Wie bereits ausgeführt, tritt eine starke Erhöhung der Reaktionsgeschwindigkeit bei Temperaturen von über 300°C ein, wobei die Polymerisationsneigung ungesättigter Kohlenwasserstoffe durch die Anwesenheit von Metallverbindungen, insbesondere der Übergangsgruppe noch weiter wesentlich begünstigt wird. Es liegt daher ein besonderes Interesse vor, gerade diese Hochtemperaturreaktionen zu behindern, da sie zur verstärkten Bildung von unverbranntem Kohlenstoff und hochmolekularen teerigen Kohlenwasserstoffverbindungen (enthaltend meist auch polycyclische Aromaten) führen, welche canzerogene Eigenschaften aufweisen können.The object of the invention is to provide an additive for heating oils and diesel fuels and other liquid fuels, which hinders the polymerization at temperatures of in particular 300 ° C. and above. As already stated, there is a sharp increase in the reaction rate at temperatures above 300 ° C., the tendency of unsaturated hydrocarbons to polymerize being significantly further favored by the presence of metal compounds, in particular the transition group. It is therefore of particular interest to hinder precisely these high-temperature reactions, since they lead to the increased formation of unburned carbon and high-molecular tarry hydrocarbon compounds (which usually also contain polycyclic aromatics), which can have cancerogenic properties.
Um eine Polymerisationsbehinderung auch bei Temperaturen von 300 °C und darüber ausüben zu können, dürfen sich die hierzu verwendeten Inhibitoren bei dieser Temperatur bei Normaldruck weder zersetzen noch verdampfen (Siedepunkt oder Sublimierung über 300°C). Dadurch können die für die Stabilisierung von Heizölen und Destillaten bereits bekannten Antioxydations- und Antipolymerisationsmittel für die vorliegenden Ziele nicht verwendet werden, da sie diese Bedingungen nicht erfüllen. So werden vielfach zur Lagerstabilisierung von Leicht- und Mitteldestillaten 2,4-Dimethyl-6-tert-butylphenol, 2,6-Di-tert-butylp-cresol (BHT), sterisch gehinderte Xylenole und Trimethylphenole, butylierte Hydroxyanisole (BHA), Mono-tert-butyl-hydrochinon (TBHQ), para-Cresole und aromatische Amine verwendet. Diese Inhibitoren sind nurfürTemperaturbereiche bis zu etwa 150 °C geeignet.In order to be able to hinder polymerization even at temperatures of 300 ° C and above, the inhibitors used for this purpose must neither decompose nor evaporate at this temperature at normal pressure (boiling point or sublimation above 300 ° C). As a result, the antioxidants and antipolymerizers which are already known for the stabilization of heating oils and distillates cannot be used for the present purposes since they do not meet these conditions. For example, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylp-cresol (BHT), sterically hindered xylenols and trimethylphenols, butylated hydroxyanisoles (BHA), mono are widely used for the storage stabilization of light and middle distillates -tert-butyl-hydroquinone (TBHQ), para-cresols and aromatic amines are used. These inhibitors are only suitable for temperature ranges up to about 150 ° C.
Für Kunststoffe, Schmieröle und Asphalte sind zur Stabilisierung derselben schon Oxydations-und Polymerisationsinhibitoren eingesetzt worden, die auch für höhere Temperaturbelastungen bestimmt sind. Ein für hitzebeständige Gummiartikel bekanntes Alterungsschutzmittel ist z.B. das Zinksalz des 2-Mercapto-benzimidazols. Dieser Inhibitor wird aber ebenfalls bei Temperaturen von 300 °C zersetzt und ist für höhere Temperaturen nicht geeignet.Oxidation and polymerization inhibitors, which are also intended for higher temperature loads, have already been used to stabilize plastics, lubricating oils and asphalts. An anti-aging agent known for heat resistant rubber articles is e.g. the zinc salt of 2-mercapto-benzimidazole. However, this inhibitor is also decomposed at temperatures of 300 ° C and is not suitable for higher temperatures.
Der US-A-2 697 033 ist als bekannt zu entnehmen, Ölen zur Lagerstabilisierung Zn-Dizyklohexyldithiophosphat und Ca-Petroleumsulfonat beizumengen. Allerdings ist das thermisch-oxydative Zersetzungsverhalten des Zn-Dizyklohexyldithiophosphats so ungünstig, dass die Inhibitorfunktion nicht erfüllt wird. Der Zersetzungsbeginn liegt bei Normaldruck, bei 106 Pa und bei 5 x 106 Pa weit unter 300 °C.US Pat. No. 2,697,033 is known to include Zn-dicyclohexyldithiophosphate and Ca-petroleum sulfonate in oils to stabilize the storage. However, the thermal-oxidative decomposition behavior of the Zn-dicyclohexyldithiophosphate is so unfavorable that the inhibitor function is not fulfilled. The start of decomposition is at normal pressure, at 10 6 Pa and at 5 x 10 6 Pa far below 300 ° C.
In der französischen Veröffentlichung A 1 282216 werden C8-12A1kylphenole beschrieben, welche zur Herstellung öllöslicher Erdalkalisalze dienen. Es muss sich dabei selbstverständlich um reaktionsfähige Phenole, bevorzugt Monoalkylphenole, handeln, die demzufolge als Oxidations-und Polymerisationsinhibitoren ungeeignet sind. Octyl- bis Dodecylphenole weisen bei 300 °C einen Dampfdruck in der Grössenordnung von 101 000 Pa auf, was bedeutet, dass sie vollständig oder zu einem beträchtlichen Teil bei dieser Temperatur verdampfen und daher zur polymerisationsbehindernden Katalyse bei dieser Temperatur ungeeignet sind.In the French publication A 1 282216 C 8 - 12 are described A1kylphenole which serve oil-soluble for the preparation of alkaline earth metal salts. Of course, these must be reactive phenols, preferably monoalkylphenols, which are consequently unsuitable as oxidation and polymerization inhibitors. At 300 ° C, octyl- to dodecylphenols have a vapor pressure of the order of 101,000 Pa, which means that they evaporate completely or to a considerable extent at this temperature and are therefore unsuitable for polymerization-inhibiting catalysis at this temperature.
Die GB-A-800445 zeigt die Verwendung von Mg-Naphtenat und feuerfesten Oxiden, wie z. B. Siliciumoxid. Derartige Mischungen sind aber mit Nachteilen behaftet und nicht geeignet, die gewünschte Wirkung hervorzubringen.GB-A-800445 shows the use of Mg naphthenate and refractory oxides such as e.g. B. silicon oxide. However, such mixtures have disadvantages and are not suitable for producing the desired effect.
Gemäss vorliegender Erfindung ist der Zusatz mit verbrennungsfördernder und russhemmender Wirkung zu Heizölen, Dieselkraftstoffen und sonstigen flüssigen Brenn- und Treibstoffen dadurch gekennzeichnet, dass die verbrennungskatalytisch wirksamen öllöslichen und/oder öldispergierbaren Verbindungen von Erdalkalien solche des Calziums, Strontiums und/oder Bariums sind und dass als Inhibitor ein Oxidations- und Polymerisationsinhibitor auf Basis sterisch behinderter hitzestabiler Alkylphenole mit einem durchschnittlichen Molekulargewicht von 280 oder auf Basis von N-Phenylnaphtylamin (Molgewicht 219) enthalten ist, wobei der Inhibitor eine Hitzebeständigkeit aufweist, so dass er infolge seines Dampfdruckes und/oder seiner Zersetzungstemperatur zumindest kurzzeitig bei Normaldruck Temperaturen von 300°C und darüber ohne Verlust seiner polymerisationshindernden Wirkung aussetzbar ist. Nach einem weiteren Merkmal der Erfindung beträgt das Gewichtsverhältnis Metall : Inhibitor = 1 : 0,1 bis 10.According to the present invention, the addition with combustion-promoting and soot-inhibiting effect to heating oils, diesel fuels and other liquid fuels is characterized in that the combustion-catalytically active oil-soluble and / or oil-dispersible compounds of alkaline earths are those of calcium, strontium and / or barium and that as Inhibitor is an oxidation and polymerization inhibitor based on sterically hindered heat-stable alkylphenols with an average molecular weight of 280 or based on N-phenylnaphtylamine (molecular weight 219), the inhibitor having a heat resistance so that it due to its vapor pressure and / or its decomposition temperature temperatures of 300 ° C and above can be exposed at least briefly at normal pressure without losing its polymerization-inhibiting effect. According to a further feature of the invention, the weight ratio metal: inhibitor = 1: 0.1 to 10.
Erfindungsgemässe flüssige Brenn- und Treibstoffe, insbesondere solche mit Siedeende bei Normaldruck von über 300°C, wie Heizöle und Dieselkraftstoffe, sind dadurch gekennzeichnet, dass sie den zuvor beschriebenen Zusatz enthalten. Der Metallgehalt in dem flüssigen Brenn- und Treibstoff kann erfindungsgemäss 0,1 bis 1000 Gewichtsteile per Million Gewichtsteile der genannten Brenn- und Treibstoffe betragen.Liquid fuels according to the invention, in particular those with a boiling end at normal pressure above 300 ° C., such as heating oils and diesel fuels, are characterized in that they contain the additive described above. According to the invention, the metal content in the liquid fuel and propellant can be 0.1 to 1000 Ge parts by weight per million parts by weight of the fuels mentioned.
Durch den erfindungsgemässen Zusatz wird einerseits die Lagerfähigkeit der genannten Brennstoffe verbessert und andererseits werden auch die vorbeschriebenen Polymerisationen, welche bei Temperaturen von über 300°C gewaltig beschleunigtwerden, wirksam inhibiert. Gleichzeitig wird der Vorteil einer vollständigeren Verbrennung auch bei geringerem Luftüberschuss erreicht. Dies ist um so wichtiger, als der vorgenannte Trend zur Verwendung von schwereren Schnitten und Produkten aus Konversionsanlagen, insbesondere katalytischen und thermischen Krackern sowie Verkokungsanlagen, bei Heizölen und Dieselkraftstoffen ständig zunimmt.The addition according to the invention on the one hand improves the shelf life of the fuels mentioned and on the other hand also effectively inhibits the polymerizations described above, which are accelerated enormously at temperatures of over 300 ° C. At the same time, the advantage of more complete combustion is achieved even with less excess air. This is all the more important since the aforementioned trend towards using heavier cuts and products from conversion plants, in particular catalytic and thermal crackers and coking plants, in heating oils and diesel fuels is constantly increasing.
Die gemäss vorliegender Erfindung eingesetzten Polymerisationsinhibitoren sind auch bei Temperaturen von über 300°C wirksam. Sie sind bei solchen Hitzeeinwirkungen nicht nur so lange thermisch stabil, als das zu verbrennende Kohlenwasserstofftröpfchen die Verbrennungszone durchwandert, sondern sie üben auch vorteilhafterweise bei den üblichen normalen Lagertemperaturen einen wirksamen Oxydationsschutz für Heizöle und Dieselkraftstoffe aus. Solche Inhibitoren sind hochsiedende Phenole mit längerkettigen, sterisch hindernden Alkylgruppen wie z.B. Nonyle. Auch die höhermolekulare organische Aminverbindung N-Phenyl-2-naphtylamin, erfüllt die vorliegende Bedingung. In der Praxis ist selbstverständlich stets auf etwaige cancerogene Wirkungen zu achten und die gesundheitsunschädlichen Zusätze müssen vorgezogen werden, obwohl normalerweise Heizöle und Dieselkraftstoffe weder mit der Haut noch mit Nahrung in Berührung kommen sollten.The polymerization inhibitors used according to the present invention are also effective at temperatures above 300 ° C. They are not only thermally stable under the effects of heat for as long as the hydrocarbon droplet to be burned passes through the combustion zone, but they also advantageously provide effective protection against oxidation for heating oils and diesel fuels at the normal normal storage temperatures. Such inhibitors are high boiling phenols with longer chain, sterically hindering alkyl groups such as e.g. Nonyle. The higher molecular weight organic amine compound N-phenyl-2-naphthylamine also fulfills the present condition. In practice, of course, any carcinogenic effects must always be observed and the harmful additives must be preferred, although heating oils and diesel fuels should normally not come into contact with the skin or with food.
Inhibitoren auf der Basis hochalkylierter oder polymerer sterisch behinderter Phenolverbindungen haben sich als besonders wirtschaftlich herausgestellt und bringen in vorteilhafter Weise auch keinerlei Schadstofferhöhungen durch S02/ S03 oder Stickoxyde, Phosphorverbindungen etc. im Abgas.Inhibitors based on highly alkylated or polymeric sterically hindered phenol compounds have proven to be particularly economical and advantageously do not result in any increases in pollutants by SO 2 / SO 3 or nitrogen oxides, phosphorus compounds etc. in the exhaust gas.
Die nachstehenden Beispiele sollen die vorliegende Erfindung weiter erläutern.The following examples are intended to further illustrate the present invention.
Dunkles Heizöl mit den nachstehenden Analysendaten wird mit und ohne Zusatz gemäss dieser Erfindung in einem Pieren Kessel mit Olymp 8D und Unitherm mat 5 Brennern verheizt.
Bei der Verbrennung dieses nichtadditivierten Heizöles mit dem Olymp-Brenner betrug die Russzahl nach Bacharach 3 bei einer Luftzahl von 1,4. Beim Unitherm-Brenner wurde bei gleicher Luftzahl eine Russzahl von 3,3 gemessen. Die Kesselwirkungsgrade, gemessen mit der Wärmemengenmesseinrichtung betrugen 76,0-76,3% bzw. 75,8-76,2% bei den genannten Brennern.When this non-additive heating oil was burned with the Olymp burner, the soot number according to Bacharach was 3 with an air number of 1.4. A soot number of 3.3 was measured for the Unitherm burner with the same air ratio. The boiler efficiency, measured with the heat quantity measuring device, was 76.0-76.3% and 75.8-76.2% for the burners mentioned.
Durch Zugabe von 1 Gewichtsteil eines Additives nachstehender Zusammensetzung zu 1000 Gewichtsteilen dieses dunklen Heizöles verbesserte sich bei gleicher Luftzahl (1,4) die Russzahl beim Olymp-Brenner auf 1,5 und beim Unitherm-Brenner sogar auf 1,2. Die Kesselwirkungsgrade des additivierten Heizöles wurden bei Verwendung der gleichen Wärmemesseinrichtung mit 79,5-80,0% (Olymp-Brenner) bzw. 82,0-83,0% (Unitherm-Brenner) festgestellt. Der mittlere Wirkungsgradgewinn betrug durch die Additivierung 3,6 bzw. 6,5%.By adding 1 part by weight of an additive of the following composition to 1000 parts by weight of this dark heating oil, the soot number for the Olymp burner improved to 1.5 for the same air ratio (1.4) and even to 1.2 for the Unitherm burner. The boiler efficiency of the additive heating oil was found to be 79.5-80.0% (Olymp burner) and 82.0-83.0% (Unitherm burner) when using the same heat measuring device. The average gain in efficiency was 3.6 and 6.5% due to the additives.
Die Zusammensetzung des erfindungsgemässen Additives war:
Extraleichtes helles Heizöl mit nachstehenden Analysedaten wird mit und ohne Zusatz gemäss Erfindung in einem Vossmann, Duo Parola-E, Stahlheizkessel mit einem Weishaupt Ölbrenner Typ WL 2/3 bei einer Wärmeleistung von max. 81 kW verbrannt.
Bei der Verbrennung dieses Mitteldestillates ohne Additiv wurde bei einem Abgasgehalt von 12,3-12,4% C02, 16,4% C02 + 02, unter 0,01 % CO eine Russziffer nach Bacharach von 2,9-32, festgestellt. Bei 12,6% C02, 16,1-16,2% C02 + 02, unter 0,01% CO in den Rauchgasen betrug die Russziffer 4.When this middle distillate was burned without an additive, a soot number according to Bacharach of 2.9-32 with an exhaust gas content of 12.3-12.4% C0 2 , 16.4% C0 2 + 0 2 , detected. With 12.6% C0 2 , 16.1-16.2% C0 2 + 0 2 , under 0.01% CO in the flue gases, the soot number was 4.
Durch Zugabe eines Additives nachstehender Zusammensetzung im Verhältnis von 1 Gew.Teil Zusatz zu 2500 Gew.Teilen extraleichtes Heizöl wurde bei analogen Verbrennungsbedingungen die Russzahl bei 12,3-12,4% C02 und 16,4% C02 + 02, unter 0,01 % CO im Abgas auf durchschnittlich 1,06 reduziert, d.h. um 2 Punkte verbessert. Bei 12,6% C02, 16,1-16,2% C02 + 02, unter 0,01% CO im Rauchgas betrug die Russzahl im Mittelwert 1,63, d. h. eine Verbesserung von ca. 2,4 Punkten.By adding an additive of the following composition in the ratio of 1 part by weight of addition to 2500 parts by weight of extra-light heating oil, the soot number at 12.3-12.4% CO 2 and 16.4% CO 2 + 0 2 was reduced under analogous combustion conditions 0.01% CO in the exhaust gas reduced to an average of 1.06, ie improved by 2 points. At 12.6% C0 2 , 16.1-16.2% C0 2 + 0 2 , under 0.01% CO in the flue gas, the soot number averaged 1.63, ie an improvement of approx. 2.4 points.
Im Additiv waren enthalten:
- Bariumpetrolsulfonat/Bariumcarbonat
- mit einem Gesamtgehalt von 3,35 Gew.-% Ba
- Ferrocen mit einem Gesamtgehalt
- von 2,10 Gew.-% Fe
- Alkyliertes sterisch
- gehindertes Phenol mit einem
- Mol-Gewicht von 280 und einem
- Dampfdruck von (36 000 Pa)
- 270 Torr bei 300°C 5,00 Gew.-%
- Aromatische Lösungsmittel auf 100%
- Barium petrol sulfonate / barium carbonate
- with a total content of 3.35% by weight Ba
- Ferrocene with a total content
- of 2.10 wt% Fe
- Alkylated steric
- hindered phenol with one
- Mol weight of 280 and one
- Vapor pressure of (36 000 Pa)
- 270 torr at 300 ° C 5.00% by weight
- Aromatic solvents to 100%
Gasöl mit nachfolgenden Analysedaten wurden unter den Bedingungen des Beispiels 2 mit und ohne Additiv verbrannt.
Dieses Gasöl entspricht den europäischen Vorschriften zum Einsatz als Dieselkraftstoff.This gas oil complies with the European regulations for use as diesel fuel.
Dem Gasöl wurden folgende erfindungsgemässe Additive zugegeben, wobei alkyliertes Phenol gemäss Beispiel 1 und 2, sterisch gehinderte tertnonyl-Cresole, N-Phenyl-2-naphtylamine und andere hochverdampfende Polymerisations- und Oxydationsinhibitoren mit einem Siedepunkt (Siedebereich) von über 300 °C bei Normaldruck enthalten waren. Die Zugabe des fertigen Additivs erfolgte jeweils mit 1 Gew.Teil Zusatz zu 2000 Gew.Teilen Gasöl. Bei den nachfolgenden Metallgehalten im erfindungsgemässen Zusatz wurden folgende Russzahlverbesserungen erzielt:
Es ist deutlich erkennbar, dass alle Additivkombinationen die vollständigere Verbrennung wesentlich begünstigen und die ursprünglichen Russzahlen von 3-4 drastisch -teilweise auf unter 1 - reduziert werden konnten. Hiedurch können russärmere Verbrennungsbedingungen auch bei verringertem Luftüberschuss mit entsprechender Verbesserung des Wärmewirkungsgrades erzielt werden.It can be clearly seen that all additive combinations significantly favor the more complete combustion and that the original soot numbers could be drastically reduced from 3-4, partly to less than 1. In this way, poorer combustion conditions can be achieved even with a reduced excess of air with a corresponding improvement in the thermal efficiency.
Die erfindungsgemässen Polymerisations- und Oxydationsinhibitoren mit Temperaturbeständigkeit von über 300 °C ergeben auch sehr gute Alterungsschutzwirkungen bei niedrigeren (Lager-)-Temperaturen. Es wurde ein Coker-Gasöl mit folgenden Analysedaten eingesetzt:
Dieses Coker-Gasöl (ohne Additiv) wurde dem eingangs beschriebenen beschleunigten Alterungstext bei 149°C (300° Fahrenheit) 90 Minuten unterworfen. Die Farbzahl ergab 9. Bei Anwesenheit von Ferrocen in einer solchen Menge, dass der Fe-Gehalt im Produkt 15 ppm betrug, wurde bei gleicher beschleunigter Alterung die Farbzahl auf 14, bei Anwesenheit von 15 ppm Mangan (aus MMT) auf 16 und bei 15 ppm Kupfer (aus Kupfernaphtenat) auf 18 erhöht.This coker gas oil (without additive) was subjected to the accelerated aging text described above at 149 ° C (300 ° Fahrenheit) for 90 minutes. The color number was 9. In the presence of ferrocene in such an amount that the Fe content in the product was 15 ppm, the color number became 14 with the same accelerated aging, to 16 in the presence of 15 ppm manganese (from MMT) and in 15 ppm copper (from copper naphtenate) increased to 18.
Durch Zugabe erfindungsgemässer Additive mit jeweils 3 Gew.-% Eisen (einmal aus Ferrocen, das andere Mal aus Eisennaphtenat) sowie 6 Gew.-% alkylierte Phenole gemäss Beispiel 1 und 2 als Inhibitor, Rest auf 100% Schwerpetroleumschnitt, im Verhältnis von 1 Gew.Teil Additiv auf 1000 Gew.Teile Coker-Gasöl wurde für den Vergleichstest mit dem erfindungsgemässen Zusatz wiederum ein Fe-Gehalt von 15 ppm im Produkt eingestellt. Der gleiche beschleunigte Alterungstest wie zuvor ergab bei diesen additivierten Coker-Gas- ölen Farbzahlen von 3-4.By adding additives according to the invention, each with 3% by weight of iron (one from ferrocene, the other time from iron naphtenate) and 6% by weight of alkylated phenols according to Examples 1 and 2 as inhibitors, the remainder to 100% heavy petroleum cut, in a ratio of 1% by weight Part of the additive per 1000 parts by weight of coker gas oil was again adjusted to an Fe content of 15 ppm in the product for the comparison test with the addition according to the invention. The same accelerated aging test as before gave color numbers of 3-4 for these additive coker gas oils.
Bei Verschärfung der Alterungsbedingungen auf die doppelte Einsatzzeit 180 Minuten bei 1490C (300° Fahrenheit) wurden Farbzahlen von 5 gefunden. Es zeigte sich, dass durch Verwendung der erfindungsgemässen Zusätze auch bei Mitteldestillaten aus thermischer Konversion die gewünschte Alterungszahl von unter 7 erreicht werden konnte.When the aging conditions were tightened to double the operating time of 180 minutes at 1490C (300 ° Fahrenheit), color numbers of 5 were found. It was found that by using the additives according to the invention, the desired aging number of less than 7 could be achieved even with middle distillates from thermal conversion.
Das im Beispiel 4 beschriebene nichtadditivierte Coker-Gasöl wurde in Lastkraftwagen als Dieselkraftstoff verwendet. Ein praktischer Betrieb dieser Kraftfahrzeuge war mit dem Produkt jedoch nicht möglich, da diese Dieselmotore nicht nur bei Vollast, sondern auch im Normalbetrieb sehr starke und unzumutbare Rauchentwicklungen zeigten, was durch den hohen Gehalt an Aromaten und ungesättigten Kohlenwasserstoffen bedingt sein dürfte.The non-additive coker gas oil described in Example 4 was used in trucks as diesel fuel. Practical operation of these motor vehicles was not possible with the product, however, as these diesel engines showed very strong and unreasonable smoke emissions not only at full load, but also during normal operation, which may be due to the high content of aromatics and unsaturated hydrocarbons.
Ein erfindungsgemässes Additiv, bestehend aus 15 Gew.-% MMT, 20 Gew.-% alkylierte Phenole gemäss beispiel 1 und 2 und 65 Gew.-% paraffinbasischem Petroleum wurde im Verhältnis von 1 Gew.Teil Additiv zu 700 Gew.Teilen Coker-Gasöl zugegeben. Der Mangangehalt betrug 52,8 ppm, der an hochsiedenden alkylierten Phenolen 28,6 ppm im Coker-Gasöl. Die Rauchentwicklung der damit betriebenen Dieselmotore wurde drastisch reduziert und betrug durchschnittlich 20 Hartridge Einheiten. Die Rückstände in den Verbrennungszylindern der damit betriebenen Motoren waren auch bei mehrmonatlicher Verwendung vernachlässigbar und die Einspritzung in ausgezeichnetem Zustand.An additive according to the invention, consisting of 15% by weight of MMT, 20% by weight of alkylated phenols according to Examples 1 and 2 and 65% by weight of paraffin-based petroleum, was used in a ratio of 1 part by weight of additive to 700 parts by weight of coker gas oil admitted. The manganese content was 52.8 ppm, that of high-boiling alkylated phenols 28.6 ppm in the coker gas oil. The smoke development of the diesel engines operated with it was drastically reduced and averaged 20 Hartridge units. The residues in the combustion cylinders of the engines operated with it were negligible even after several months of use and the injection in excellent condition.
Rückstandsheizöle enthaltend schwere Anteile aus Visbreakern hatten folgende Analysedaten:
Die russarme Verbrennung dieses additivfreien Rückstandsöles war nur mit sehr grossem Luftüberschuss und genau regulierbaren Brennern, meist mit Wasserdampf-Einspritzung möglich.The soot-free combustion of this additive-free residue oil was only possible with a very large excess of air and precisely adjustable burners, mostly with water vapor injection.
Es wurden diesem schweren Rückstandsöl 100 ppm Mangan (aus Mangannaphtenat) sowie durch Flammhydrolyse von Siliziumtetrachlorid gewonnenes Siliziumdioxyd mit einer Oberfläche nach BET von ca. 200 (Aerosil 200) in einer Menge von 50 ppm plus Aluminiumoxyd mit einer Oberfläche nach BET von ca. 100 (Aluminiumoxyd-C) ebenfalls in einer Menge von 50 ppm zugegeben.This heavy residual oil was treated with 100 ppm manganese (from manganese naphtenate) and silicon dioxide obtained by flame hydrolysis of silicon tetrachloride with a BET surface area of approx. 200 (Aerosil 200) in an amount of 50 ppm plus aluminum oxide with a BET surface area of approx. 100 ( Aluminum oxide-C) also added in an amount of 50 ppm.
Die russarme Verbrennung in normalen Industriebrennern war bei Luftzahlen von 1,2 und darunter ohne Schwierigkeiten möglich, wenn das vorstehend additivierte Rückstandsöl zum Einsatz gelangte.The soot-free combustion in normal industrial burners was possible without difficulty at air ratios of 1.2 and below if the above-added residual oil was used.
Die an der Oberfläche der hochdispersen Kieselsäure befindlichen Silanolgruppen sowie analoge Aluminiumhydroxyde beim hochdispersen Aluminiumoxyd dürften für die Polymerisationsinhibierung bei Temperaturen von über 300 °C verantwortlich sein, während das Mangan die Verbrennung von Kohlenstoff bzw. kohlenstoffangereicherten Partikeln in der kälteren Zone der Verbrennung katalytisch begünstigt haben dürfte. Es zeigt sich damit, dass die anorganischen Polymerisationsinhibitoren gemäss Erfindung für vorliegende Zwecke ebenfalls vorteilhaft eingesetzt werden können.The silanol groups on the surface of the highly disperse silica as well as analogous aluminum hydroxides in the highly disperse aluminum oxide are likely to be responsible for the polymerization inhibition at temperatures above 300 ° C, while the manganese may have catalytically favored the combustion of carbon or carbon-enriched particles in the colder zone of the combustion . It shows that the inorganic polymerization inhibitors according to the invention can also be used advantageously for the present purposes.
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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AT437981A AT373274B (en) | 1981-10-12 | 1981-10-12 | ADDITION WITH COMBUSTION-PROTECTING AND SOOT-RESISTING EFFECT OF FUEL OILS, DIESEL FUELS AND OTHER LIQUID FUELS AND LIQUIDS, AND LIQUID FUEL AND FUELS WITH THIS ADDITION |
AT4379/81 | 1981-10-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0078249A1 EP0078249A1 (en) | 1983-05-04 |
EP0078249B1 true EP0078249B1 (en) | 1987-10-28 |
Family
ID=3563223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19820890134 Expired EP0078249B1 (en) | 1981-10-12 | 1982-09-24 | Additive with a combustion promoting and soot inhibiting activity for furnace oils, diesel fuels and other liquid combustion and fuel substances, as well as the aforesaid liquid combustion and fuel substances |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0078249B1 (en) |
AT (1) | AT373274B (en) |
CA (1) | CA1188891A (en) |
DE (1) | DE3277537D1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5360459A (en) | 1991-05-13 | 1994-11-01 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
US5376154A (en) | 1991-05-13 | 1994-12-27 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organometallic complexes |
US5534039A (en) | 1991-05-13 | 1996-07-09 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK152925C (en) * | 1985-06-28 | 1989-04-10 | Sparol Int Aps | ADDITIVE TO LIQUID FUEL |
EP0579339B1 (en) * | 1985-08-16 | 1997-06-04 | The Lubrizol Corporation | Fuel products |
US4690687A (en) * | 1985-08-16 | 1987-09-01 | The Lubrizol Corporation | Fuel products comprising a lead scavenger |
FR2616795B1 (en) * | 1987-06-19 | 1989-10-27 | Inst Francais Du Petrole | IMPROVED PROCESS FOR PRODUCING HEAT BY COMBUSTION OF HEAVY FUEL |
ATE107347T1 (en) * | 1988-01-27 | 1994-07-15 | Lubrizol Corp | FUEL COMPOSITION. |
US5160350A (en) * | 1988-01-27 | 1992-11-03 | The Lubrizol Corporation | Fuel compositions |
US4908045A (en) * | 1988-12-23 | 1990-03-13 | Velino Ventures, Inc. | Engine cleaning additives for diesel fuel |
GB2239258A (en) * | 1989-12-22 | 1991-06-26 | Ethyl Petroleum Additives Ltd | Diesel fuel compositions containing a manganese tricarbonyl |
US5944858A (en) * | 1990-09-20 | 1999-08-31 | Ethyl Petroleum Additives, Ltd. | Hydrocarbonaceous fuel compositions and additives therefor |
DE69004692T2 (en) * | 1990-09-20 | 1994-03-10 | Ethyl Petroleum Additives Ltd | Hydrocarbon compositions and additives therefor. |
EP0482253A1 (en) * | 1990-10-23 | 1992-04-29 | Ethyl Petroleum Additives Limited | Environmentally friendly fuel compositions and additives therefor |
TW230781B (en) * | 1991-05-13 | 1994-09-21 | Lubysu Co | |
IT1254456B (en) * | 1992-02-14 | 1995-09-25 | Basf Italia | BRAND-DENATURING COMPOSITION PARTICULARLY SUITABLE FOR MARKING AND ENENATURING COMBUSTIBLE BITUMES OR RELATED PRODUCTS. |
US5551957A (en) * | 1992-05-06 | 1996-09-03 | Ethyl Corporation | Compostions for control of induction system deposits |
US5511517A (en) * | 1994-02-10 | 1996-04-30 | Ethyl Corporation | Reducing exhaust emissions from otto-cycle engines |
CA2205143C (en) * | 1996-05-14 | 2003-07-15 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
GB2321906A (en) * | 1997-02-07 | 1998-08-12 | Ethyl Petroleum Additives Ltd | Fuel additive for reducing engine emissions |
DE19701961A1 (en) * | 1997-02-22 | 1998-12-24 | Adolf Dipl Chem Metz | Bio-catalyst additive for liquid hydrocarbon fuels |
ATE328986T1 (en) * | 1999-09-01 | 2006-06-15 | Ass Octel | FUEL ADDITIVE FOR VALVE SEAT BACKBACK PREVENTION |
IT1318868B1 (en) | 2000-08-03 | 2003-09-10 | Cesare Pedrazzini | ADDITIVE TO REDUCE THE PARTICULATE IN THE EMISSIONS RESULTING FROM THE COMBUSTION OF DIESEL AND FUEL OIL AND FUEL COMPOSITION |
US7300477B2 (en) * | 2003-08-14 | 2007-11-27 | Afton Chemical Corporation | Method and fuel additive including iron naphthenate |
US7332001B2 (en) * | 2003-10-02 | 2008-02-19 | Afton Chemical Corporation | Method of enhancing the operation of diesel fuel combustion systems |
GB0700534D0 (en) | 2007-01-11 | 2007-02-21 | Innospec Ltd | Composition |
EP2370557A1 (en) | 2008-12-29 | 2011-10-05 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
CN102337169B (en) * | 2010-07-16 | 2013-07-03 | 甘肃黑马石化工程有限公司 | Multicomponent slag-removing and ash-cleaning energy saving composition for boilers and preparation technology thereof |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2622671A (en) * | 1949-07-07 | 1952-12-23 | Nat Aluminate Corp | Soot remover |
US2697033A (en) * | 1950-03-28 | 1954-12-14 | Gulf Research Development Co | Stable fuel oil compositions |
US2639227A (en) * | 1950-09-02 | 1953-05-19 | Shell Dev | Anticlogging fuel oil compositions |
GB800445A (en) * | 1956-08-17 | 1958-08-27 | Exxon Research Engineering Co | Improved fuel for use in gas turbine plants |
FR1282216A (en) * | 1959-12-15 | 1962-01-19 | Exxon Research Engineering Co | Process for the manufacture of additives soluble in petroleum oils |
DK130016B (en) * | 1973-03-15 | 1974-12-09 | N Ringsted | Use of oil-soluble alkaline earth metal salts as an additive to fuel oil. |
-
1981
- 1981-10-12 AT AT437981A patent/AT373274B/en not_active IP Right Cessation
-
1982
- 1982-09-24 DE DE8282890134T patent/DE3277537D1/en not_active Expired
- 1982-09-24 EP EP19820890134 patent/EP0078249B1/en not_active Expired
- 1982-10-08 CA CA000413082A patent/CA1188891A/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5360459A (en) | 1991-05-13 | 1994-11-01 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
US5376154A (en) | 1991-05-13 | 1994-12-27 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organometallic complexes |
US5534039A (en) | 1991-05-13 | 1996-07-09 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
Also Published As
Publication number | Publication date |
---|---|
EP0078249A1 (en) | 1983-05-04 |
DE3277537D1 (en) | 1987-12-03 |
ATA437981A (en) | 1983-05-15 |
CA1188891A (en) | 1985-06-18 |
AT373274B (en) | 1984-01-10 |
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