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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 point at normal pressure above 300 ° C., and liquid fuels with such an additive.
• Excess air is known to be one of the most important factors affecting the thermal efficiency of a combustion. plant influenced. The more excess air is unnecessarily heated, the greater the waste heat losses. Through the minimie The loss of usable heat is reduced by the excess air, 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.
• 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 finely divided droplets (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. While this Droplets migrate through the combustion zone, their size continuously decreases until the volatile constituents have evaporated (and burned).
• a small or large remnant of non-volatile constituents remains, which consist of high-polymer organic compounds, carbon and impurities.
• hydrocarbons When hydrocarbons are heated strongly, 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 as a result of 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.
• NMT methylcyclopentadienyl manganese tricarbonyl
• ferrocene dicyclopenta dienyl 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 ingress of 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 to 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 also determined according to ASIM (D - 1500 - 58 T) before and after aging, which also allows a relative evaluation of the stability.
• combustion can be improved by catalytically active oil-soluble and / or oil-dispersible metal compounds. but at the same time this is 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.
• Polymerization and oxidation inhibitors are known per se and are used in a wide variety of products such as e.g. Food, cosmetics, plastics, rubber and also used in mineral oil derivatives. It has been shown that these ingredients for promoting combustion are largely ineffective in the products in question here. In the case of 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 customary storage temperatures. A temperature load 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 of over 300 ° C. the tendency of unsaturated hydrocarbons to polymerize being significantly further favored by the presence of metal compounds, in particular the transition group.
• the inhibitors did not decompose or 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.
• 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), sterically hindered xylenols and trimethylphenols, butylated hydroxyanisoles (BHA) are often used to stabilize the storage of light and middle distillates.
• Mono-tert-butylhydroquinone (TBHQ), para-cresols and aromatic amines are used. These inhibitors are only suitable for temperature ranges up to approximately 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.
• the additive according to the invention is primarily characterized in that it comprises one or more oil-soluble and / or dispersible compounds of transition metals and / or alkaline earths and one or more inhibitors against polymerization and oxidation of hydrocarbons, these inhibitors being heat-stable and due to their vapor pressure and / or their decomposition temperature can be exposed to temperatures of 300 P C and above at normal pressure for at least a short time without losing their polymerization-inhibiting effect.
• the liquid fuel and fuel according to the invention is characterized in that the metal content is 0.1 to 1000 parts by weight per million parts by weight of the fuels mentioned. Further preferred embodiments of the invention are characterized in the remaining subclaims.
• 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 air excess. 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. With such heat effects, they are not only thermally stable as long as the hydrocarbon droplet to be burned travels 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 e.g. high-boiling phenols with longer-chain, sterically hindering alkyl groups, e.g. Nonyls.
• higher molecular weight organic amine compounds such as e.g. N-phenyl-2-naphthylamine, meet the present condition.
• any carcinogenic effects must always be observed and the additives that are harmful to health must be preferred, although heating oils and diesel fuels should normally not come into contact with the skin or with food.
• Selected metal (eg zinc, molybdenum) alkyl dithiophosphates, dithiocarbamates and imidazoles, as well as other metal compounds, can also meet the thermal stability requirements as such suitable inhibitors.
• 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 additives, according to the invention in a Voßmann, Duo Paro-1a-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 + O 2 , under 0.01% CO in the exhaust gas reduced to an average of 1.06, ie improved by 2 points.
• the average number of soot was 1.63, ie one Improvement of approximately 2.4 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 tert-nonyl-cresols, N-phenyl-2-naphthylamines and other highly evaporative polymerization and oxidation inhibitors with a boiling point (boiling range) of over 300 9 C at normal pressure were included.
• the finished additive was added with 1 part by weight of addition to 2,000 parts by weight of gas oil.
• the following improvements in the number of carbon blacks were achieved for the following metal contents in the additive according to the invention:
• the polymerization and oxidation inhibitors according to the invention with a temperature resistance of over 300 ° C. also give very good anti-aging effects at lower (storage) temperatures.
• a coker gas oil with the following analysis data was used: 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.
• additives according to the invention 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 1,000 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 additive according to the invention. The same accelerated aging test as before gave color numbers of 3-4 for these additive coker gas oils.
• 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 the 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, of the 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.
• the silanol groups on the surface of the highly disperse silicic acid as well as analogous aluminum hydroxides in the case of the highly disperse aluminum oxide are likely to contribute to the polymerization inhibition Temperatures above 300 ° C may be responsible, 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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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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Cited By (26)

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Citations (6)

• 1981
  • 1981-10-12 AT AT437981A patent/AT373274B/de not_active IP Right Cessation
• 1982
  • 1982-09-24 DE DE8282890134T patent/DE3277537D1/de not_active Expired
  • 1982-09-24 EP EP19820890134 patent/EP0078249B1/fr not_active Expired
  • 1982-10-08 CA CA000413082A patent/CA1188891A/fr not_active Expired

Patent Citations (6)

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