EP0087073B1 - Verfahren zur Verbesserung von Kraftstoffen für Dieselmotoren - Google Patents

Verfahren zur Verbesserung von Kraftstoffen für Dieselmotoren Download PDF

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Publication number
EP0087073B1
EP0087073B1 EP83101271A EP83101271A EP0087073B1 EP 0087073 B1 EP0087073 B1 EP 0087073B1 EP 83101271 A EP83101271 A EP 83101271A EP 83101271 A EP83101271 A EP 83101271A EP 0087073 B1 EP0087073 B1 EP 0087073B1
Authority
EP
European Patent Office
Prior art keywords
process according
salts
fuel
carboxylic acids
acids
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
Application number
EP83101271A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0087073A3 (en
EP0087073A2 (de
Inventor
Manfred Dr. Wildersohn
Werner Dipl.-Chem. Dewin
Bela Dr. Dipl.-Chem. Tihanyi
Jürgen Dr. Dipl.-Chem. Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wenzel and Weidmann GmbH
Ruhrchemie AG
Original Assignee
Wenzel and Weidmann GmbH
Ruhrchemie AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wenzel and Weidmann GmbH, Ruhrchemie AG filed Critical Wenzel and Weidmann GmbH
Priority to AT83101271T priority Critical patent/ATE14748T1/de
Publication of EP0087073A2 publication Critical patent/EP0087073A2/de
Publication of EP0087073A3 publication Critical patent/EP0087073A3/de
Application granted granted Critical
Publication of EP0087073B1 publication Critical patent/EP0087073B1/de
Expired legal-status Critical Current

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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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 present invention relates to a method for improving the combustion of fuels for diesel engines by adding mixtures of salts of organic acids of the lanthanoids and free carboxylic acids.
  • Diesel fuels are more susceptible to soot when burning in engines than petrol.
  • the soot indicates that the combustion process in the engine is incomplete, i. H. the generation of energy from the fuel is not fully used.
  • diesel smoke which u. a. Containing hydrocarbons and carbon monoxide is a major environmental burden. For this reason, efforts have long been made to suppress the formation of soot during the combustion of diesel fuels by adding additives and to ensure that the combustion is as complete as possible.
  • cerium soaps in which an atom of the trivalent cerium is essentially connected to three molecules of a fatty acid, by the action of a carboxylic acid with more than 8 carbon atoms on cerium hydroxide. These compounds are used as drying agents in the field of paints or varnishes and varnishes and, moreover, as combustion aids.
  • organic radical u. a. also as a combustion aid.
  • their main area of application is that of drying agents for paints and varnishes.
  • the invention consists in a method for improving the combustion of fuels for diesel engines with the aid of salts of organic acids. It is characterized in that a mixture of neutral salts of carboxylic acids and metals of atomic number 57 to 71 and free carboxylic acids is added to the fuels.
  • the process according to the invention ie the addition of neutral salts of organic acids of certain metals in combination with free carboxylic acids, leads to a perfect combustion of the diesel fuels without deposits occurring.
  • the soot number which is a measure of the completeness of the combustion of the fuel, is significantly reduced compared to fuels which have not been treated by the method according to the invention. It is particularly important that the carbon monoxide concentration and the nitrogen oxide concentration are considerably reduced by the process according to the invention.
  • the method according to the invention brings a considerable saving in fuel, depending on the speed, of at least 2%.
  • the acceleration time is reduced in the high speed range compared to fuel not provided with additives according to the invention.
  • neutral salts of carboxylic acids are understood to be those salts in which all valences of the metal are saturated by carboxylic acid residues. It is possible to use salts of a wide variety of carboxylic acids. Both aliphatic and aromatic carboxylic acids are suitable. Salts of aliphatic monocarboxylic acids, in particular aliphatic monocarboxylic acids with 4 to 10 carbon atoms, have proven successful.
  • carboxylic acids can be branched one or more times, in addition to isooctanoic acid, particular importance is attached to the carboxylic acids which have the branching in the a position, such as 2-ethylbutyric acid and 2-ethylhexanoic acid.
  • the above-mentioned isooctanoic acid means the Cg-carboxylic acid mixture containing predominantly isomeric dimethylhexanoic acid. It is obtained by hydroformylation of an industrial heptene mixture and subsequent oxidation of the hydroformylation product.
  • Carboxylic acids obtained by the addition of carbon monoxide and water to olefins after the cooking process have also proven successful. These include e.g. B. pivalic acid, 2,2-dimethylvaleric acid and neohexanoic acid.
  • Uniform salts can be used in the process according to the invention, ie salts which contain only one cation. It is also possible to use salts which contain different metals, or else mixtures of different salts. This includes mixtures of salts of the same metals and different acids from salts of different metals and the same acids and of salts of different metals and different acids. It is particularly expedient to use salts which are derived from the naturally occurring cerium earths. Cerite earths are minerals that contain the elements of atomic number 57 to 71, ie lanthanum and the so-called lanthanoids varying amounts included. Salts derived from the mineral bastnäsite, which is available in large quantities, have proven particularly useful.
  • the salts are prepared in a known manner. So one can start from the solutions of the nitrates of metals, which are reacted with the stoichiometric amount of the sodium salts of the carboxylic acids.
  • the sodium salts of the carboxylic acids are advantageously used as a solution in an organic solvent in which the reaction product, ie. H. the lanthanoid salts, is soluble. They are obtained from the solution by distilling off the solvent, further cleaning operations are not necessary.
  • the nitrates of the metals are obtained directly by digestion with nitric acid.
  • free carboxylic acids are used as a further component of the mixtures added to the diesel fuel.
  • all carboxylic acids that are soluble in the fuel for diesel engines can be used. It has proven very useful to use as carboxylic acids those acids that are present as acid residues in the salts that are part of the mixture.
  • the mixture contains 0.1 to 2 moles and in particular 0.2 to 1.5 moles of free carboxylic acids. It is particularly useful to use 0.5 to 1.0 mol of free carboxylic acid.
  • the mixtures of organic acid salts of lanthanides and free carboxylic acids used in the process according to the invention for improving combustion are added to the fuels for diesel engines in amounts such that their concentration is 5 to 200 mg of lanthanide metal or metal mixture per kg of fuel. Concentrations of 10 to 50 and based on native oils concentrations of 10 to 100 mg lanthanide metal or metal mixture per kg fuel have proven particularly useful in fuels based on mineral oil.
  • the diesel fuel used in the experiments below contains 15 mg Ce per kg as Ce (III) -2-ethylhexanoate / 2-ethylhexanoic acid mixture.
  • the basis for the tests is the ECE-15 driving cycle, which is used for exhaust gas tests in accordance with European regulations and for fuel consumption measurements in accordance with DIN 70 030.
  • the following engine is used:
  • Fuel consumption measurements are carried out at 50 km / h, 90 km / h and 120 km / h, whereby 20 measured values are averaged and the standard deviation is taken into account.
  • the measurement series is carried out with diesel fuel plus additive compared to diesel fuel without additive. With diesel fuel with additive, there is a minimum consumption of at least achieved. The maximum savings are well over 2%.
  • the influence of the additive on the acceleration time can be seen in the higher speed range as a decrease in the acceleration times, starting at 1,000 revolutions / min with a full throttle. up to 4,500 revolutions. Here, too, an average of 20 measured values is used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP83101271A 1982-02-18 1983-02-10 Verfahren zur Verbesserung von Kraftstoffen für Dieselmotoren Expired EP0087073B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83101271T ATE14748T1 (de) 1982-02-18 1983-02-10 Verfahren zur verbesserung von kraftstoffen fuer dieselmotoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3205732 1982-02-18
DE19823205732 DE3205732A1 (de) 1982-02-18 1982-02-18 Verfahren zur verbesserung der verbrennung von kraftstoffen fuer dieselmotoren

Publications (3)

Publication Number Publication Date
EP0087073A2 EP0087073A2 (de) 1983-08-31
EP0087073A3 EP0087073A3 (en) 1984-04-25
EP0087073B1 true EP0087073B1 (de) 1985-08-07

Family

ID=6156021

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83101271A Expired EP0087073B1 (de) 1982-02-18 1983-02-10 Verfahren zur Verbesserung von Kraftstoffen für Dieselmotoren

Country Status (7)

Country Link
US (1) US4474579A (enrdf_load_stackoverflow)
EP (1) EP0087073B1 (enrdf_load_stackoverflow)
AT (1) ATE14748T1 (enrdf_load_stackoverflow)
BR (1) BR8300717A (enrdf_load_stackoverflow)
DE (2) DE3205732A1 (enrdf_load_stackoverflow)
IN (1) IN159185B (enrdf_load_stackoverflow)
ZA (1) ZA83961B (enrdf_load_stackoverflow)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3245882A1 (de) * 1982-12-11 1984-06-14 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur verbesserung der verbrennung fluessiger brennstoffe
US4522631A (en) * 1983-11-18 1985-06-11 Texaco Inc. Diesel fuel containing rare earth metal and oxygenated compounds
US4670020A (en) * 1984-12-24 1987-06-02 Ford Motor Company Carbon ignition temperature depressing agent and method of regenerating an automotive particulate trap utilizing said agent
ATE66957T1 (de) * 1986-09-19 1991-09-15 Rhone Poulenc Chimie Verwendung von gemischen aus seltenen erden, um kraftstoffe fuer dieselmotoren zu stabilisieren.
FR2644471B1 (fr) * 1989-03-14 1991-06-07 Atochem Procede pour ameliorer l'indice de cetane des gazoles de distillation directe
IL100669A0 (en) 1991-05-13 1992-09-06 Lubrizol Corp Low-sulfur diesel fuel containing organometallic complexes
US5360459A (en) 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5344467A (en) 1991-05-13 1994-09-06 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
TW230781B (enrdf_load_stackoverflow) 1991-05-13 1994-09-21 Lubysu Co
US5376154A (en) 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
FR2714695B1 (fr) * 1993-12-31 1996-03-22 Rhone Poulenc Chimie Procédé pour maintenir propre les circuits d'un moteur turbocompressé et pour réduire les rejets carbonés d'un tel moteur.
FR2720405B1 (fr) * 1994-05-25 1996-07-26 Rhone Poulenc Chimie Procédé pour réduire l'émission de suies d'un moteur à combustion interne, composés du lanthane et leur usage pour réduire la pollution.
US7302410B1 (en) * 2000-12-22 2007-11-27 Demandtec, Inc. Econometric optimization engine
EP1344810A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Fuel additive compositions for diesel engine equipped with a particulate trap
EP1344812A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Overbased metallic salt diesel fuel additive compositions for improvement of particulate traps
GB0606986D0 (en) * 2006-04-06 2006-05-17 Oxonica Energy Ltd Biofuels
US7867295B2 (en) 2007-08-29 2011-01-11 Baker Hughes Incorporated Branched carboxylic acids as fuel lubricity additives
US8262749B2 (en) * 2009-09-14 2012-09-11 Baker Hughes Incorporated No-sulfur fuel lubricity additive
RU2694884C1 (ru) * 2018-05-30 2019-07-17 Общество с ограниченной ответственностью "ГаммаАддитив" (ООО "ГаммаАддитив") Присадка противоизносная к топливу для реактивных двигателей "GT-2017"

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB279560A (en) * 1926-07-29 1927-10-31 Asiatic Petroleum Co Ltd Improvements in and relating to means for preventing pinking or knock in internal combustion engines
US3003859A (en) * 1956-05-31 1961-10-10 Ethyl Corp Liquified chelate gasoline additives
US2913319A (en) * 1956-08-13 1959-11-17 Gulf Research Development Co Fuel oils
US3205053A (en) * 1961-05-08 1965-09-07 Carborundum Co Fuel oil composition containing corrosion inhibiting additive
US3594138A (en) * 1968-01-02 1971-07-20 Cities Service Oil Co Smoke suppressant additives for petroleum fuels
US3762890A (en) * 1973-09-26 1973-10-02 Mooney Chemicals Stabilized polyvalent metal soap composition
FR2359199A1 (fr) * 1976-07-22 1978-02-17 Gamlen Naintre Sa Derives oleosolubles de metaux de terres rares utiles comme adjuvants de combustion dans les moteurs diesel
US4067699A (en) * 1976-12-17 1978-01-10 Union Oil Company Of California Fuel composition
US4133648A (en) * 1977-06-29 1979-01-09 Gulf Research & Development Company Organic synergists for organo-cerium (IV) anti-knock additives in lead-free fuel compositions
US4336148A (en) * 1977-09-07 1982-06-22 Ciba-Geigy Corporation Complex compound, process for their preparation, and their use
US4264335A (en) * 1978-11-03 1981-04-28 Gulf Research & Development Company Suppressing the octane requirement increase of an automobile engine
DE2930220A1 (de) * 1979-07-25 1981-01-29 Landwirtschaftskammer Schleswi Dieselkraftstoff

Also Published As

Publication number Publication date
IN159185B (enrdf_load_stackoverflow) 1987-04-04
DE3205732A1 (de) 1983-08-25
US4474579A (en) 1984-10-02
DE3360492D1 (en) 1985-09-12
EP0087073A3 (en) 1984-04-25
BR8300717A (pt) 1983-11-16
EP0087073A2 (de) 1983-08-31
ATE14748T1 (de) 1985-08-15
ZA83961B (en) 1983-11-30

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