EP1124915B1 - Glyoxal as fuel additive - Google Patents

Glyoxal as fuel additive Download PDF

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Publication number
EP1124915B1
EP1124915B1 EP99948796A EP99948796A EP1124915B1 EP 1124915 B1 EP1124915 B1 EP 1124915B1 EP 99948796 A EP99948796 A EP 99948796A EP 99948796 A EP99948796 A EP 99948796A EP 1124915 B1 EP1124915 B1 EP 1124915B1
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EP
European Patent Office
Prior art keywords
glyoxal
fuel
additive
acetalization
gasoline
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 - Lifetime
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EP99948796A
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German (de)
English (en)
French (fr)
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EP1124915A1 (en
Inventor
Horst Kief
Wolfgang F.. HÖLDERICH
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Kief Horst Dr med
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Kief Horst Dr med
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • 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, 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
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters

Definitions

  • the present invention relates to fuel additives for internal combustion device fuels, particularly for gasoline and diesel engine fuels and fuel oils, which provide a reduction in pollutant emissions and coke deposits, improved efficiency, smoother running of the engine as well as a cleaning effect on the combustion chamber of the engine.
  • Metal-ceramic catalytic converters are known to reduce this damage by means of catalytic afterburning of the engine exhausts.
  • the combustion energy released thereby cannot be used, however, for the primary process of energy production in the engine.
  • the efficiency of the catalytic converter can decrease over time leading to increased pollutant emission levels.
  • the addition of a fuel additive, prior to the combustion stage, would have distinct advantages over, or in addition to the traditional methods for handling exhaust emissions.
  • DE-PS 801 865 teaches the use of fuel additives, which can be toluene, benzene, acetone, trichlorethylene or isobutyl alcohol, besides the metal carbonyls, although the fundamental drawback of metal oxide deposits in the combustion chamber remains the same.
  • DE-AS 1 221 488 describes fuel additives consisting of methylcyclopentadienyl manganese tricarbonyl, lead tetraethyl or other organometallic compounds and organic compounds having two ester groups.
  • organic fuel additives are also recognised as constituting a part of the state-of-the-art: a mixture of an aromatic amine and a polyalkyl phenol, as shown in DE-PS 845 286; tretaarylhydrazine, diarylnitrosamine and triarylmethyl derivatives from DE-PS 505 928; aldehydes, quinones and ketones from DE-PS 612 073; ketones of formula R-CO-R', wherein R represents a ring radical and R' an aliphatic radical with at least 6 C-atoms, from United States Patent No.
  • United States Patent No. 1,973,475 describes a method for oxidation of fuels with air or oxygen at elevated temperatures, possibly in the presence of a catalyst.
  • DE-PS 699 273 discloses a method of dehydrogenation of non-flammable oils from the boiling range of diesel oils in inflammable oils with oxidising agents such as air or oxygen, ozone, peroxides, chromic acid or nitric acid at 150°-350°C, possibly at elevated pressure and preferably in presence of a catalyst.
  • the ozonization of fuels is also described in DE-PS 324 294 and DE-PS 553 943.
  • ozonides such as ethylene ozonide, or a mixture of one of the conventional fuels with an ozonide, are added to the internal combustion engine.
  • the drawback of the method is the instability of the ozonides, so that when kept for a lengthy time the availability of oxygen carriers is necessarily variable, apart from the problems of environmental pollution, which were not known at the time.
  • DE-PS 553 943 a mixture of hydrocarbons is ozonized under pressure in the presence of an oxygen carrier, such as turpentine oil, and slight amounts of ignition-promoting substances.
  • EP-A 855 436 is concerned with additives to environment compatible diesel fuels comprising natural fluid triglycerides, i, e. animal or plant fats, which are chemically totally different to the mineral oil used as fuel in the invention in suit.
  • Natural triglycerides have a very high viscosity and even may be solid at lower temperatures and therefore have to be mixed with considerable amounts of other components of a lower viscosity which on the other hand increase the cetane number to allow a proper ignition and minimize the emission of unreacted fuel.
  • Glyoxaftetraethylacetal is known to be effective in amounts higher 1 : 1.000, this literature is not concerned with the action of glyoxal or glyoxal derivates with mineral oil.
  • EP-A-30429 is concerned with the production of synthetic fuels that comprise (A) at least one alcohol with an average molecular weight of less than 160 and (B) a further organic compound with an ignition temperature of less than 450° C, which may be selected from the group of alcohols, ethers, aldehydes and nitrogen containing compounds. This compound may be glyoxaltetrabutylacetal. Conventional fuels like diesel oil may be added as additives.
  • WO-9705217-A describes the production of a homogenous catalyst be oxidizing aromatic compounds in the fuel by adding ozone. As disclosed on page 2, line 33 to page 3, line 2, the produced glyoxal molecules tend to polymerise and separate from the fuel as a solid mass which is detrimental to the catalytic process.
  • WO 9533022-A describes a method of reducing the temperature for metallic vapour phase combustion to produce a metallic vapour from different metals or metallic compounds.
  • fuel numerous different compounds are mentioned, showing that the nature of the fuel is in no way limiting to the effect.
  • the problem of the invention in suit to decrease the pollution emission of hydrocarbon fuels in combustions engines is not mentioned at all.
  • DE 1144971 there is shown the use of leadtetraethyl in addition to monocarbonic acids, to achieve boosting of the octane number.
  • DE 1271455 diketons are patented in combination with leadtetraethyl as antiknock-substances.
  • Aliphatic polyethers with the general formula R-(O-X) n -O-R') are described in the USP No. 2,655,440 as additives increasing the cetane number.
  • DE 19527423 A1 describes the ozonisation of gasoline containing benzene, wherein together with other oxidation products glyoxal is formed. This process has the disadvantage, that ozonisation apparatus in a refinery are unusual and expensive.
  • the present invention has as its object the reduction of the emission of pollutants and the consumption of fossil fuels and their derivatives.
  • the pollution of environment by the incomplete combustion sequence in combustion engines with expulsion of carbon monoxide, unburned hydrocarbons, as well as nitrogen oxide is sufficiently well known.
  • Subsequent use of catalytic converters, and the like, are a stop gap measure, at best. Thus, preference should be given to an optimization of the combustion process in the immediate energy-supplying step.
  • the present invention accomplishes this purpose in a fundamental, technically feasible and effective mode and manner.
  • pollutant emissions from combustion engines are reduced by the addition of glyoxal and glyoxal derivatives and adducts in aqueous solution to the fuel supply to the combustion engine.
  • glyoxal and glyoxal derivatives and adducts are added to the fuel.
  • different acetals and hemiacetals or a mixture thereof obtained by the acetalization of glyoxal are added to the fuel.
  • Applicant's WO 9501411 A now issued as United States Patent No. 5,762,655 describes a technique for optimizing the combustion process in internal combustion engines.
  • the ozonization products of gasoline and diesel fuels provide a catalytic effect on the combustion process with the result that unburned hydrocarbons and carbon monoxide are reduced drastically.
  • this technique has the advantage that it is highly effective.
  • it has the disadvantage that it is relatively costly since an ozonization system has to be integrated into the respective refinery plants supplying the combustion fuel.
  • the present invention has as its object to provide the same benefits achieved with the previously described ozonization process, but without the attendant expense.
  • glyoxal in aqueouss solution is used as a basic product for fuel additives in order to obtain a reduction of pollutant emission.
  • Glyoxal is obtained by oxidation from glycol in aqueous solution in industrial scale techniques.
  • glyoxal can be added to the fuel either together with flammable emulsifiers or in a chemical compound as described below.
  • this technique has the advantage that, here, a product can be used which is produced on an industrial scale and, therefore, economically and easily available; furthermore, the substances described herein are relatively stable in storage compared to the oxides which arose in the ozonization process of previous techniques and which drastically reduced the storage stability.
  • One factor to be considered in the practice of the present invention is the relative solubility of glyoxal in water when it is added to gasoline. It has been discovered, however, that a usual 40% glyoxal solution, together with a usual emulsifier consisting of esterified aliphatic compounds, can be mixed surprisingly well with gasoline if polyethyleneglycol is added. Thus, for example, 10 milliliters of a 40% glyoxal solution plus 10 milliliters of a standard, off the shelf emulsifier based on esterified aliphats (i.e.
  • the aqueous glyoxal solution as described above is even more easily soluble than in gasoline.
  • a milky cloudy fuel mixture is obtained, the phase mixture of which is considerably more stable.
  • Fuels to which this additive have been added produce in diesel engine vehicles at idle and at increased idle (10 % according to ECE-standard 1997) an average reduction of the particulate emission or coke deposit of 30 to 40% and of nitrogen oxides of 20%.
  • FIGS. 1 to 4 graphically present the average pollution emission values of a stationary engine (BMW Type 5 (525 or 528)) of tables I and II that is operated with a conventional gasoline before and after application of a glyoxal emulsion according to the present invention.
  • Fig. 1 shows the carbon monoxide (CO) values in %vol at idle.
  • CO carbon monoxide
  • aqueous glyoxal emulsion containing 4 g glyoxal in 10 ml water to 40 I gasoline fuel, which corresponds to a ratio of additive to fuel 1:10000, i. e. 0,1 ⁇ vol a reduction of 50 % from 0,02 %vol to 0,01 %vol CO is obtained.
  • Fig. 2 shows the emission values of hydrocarbons (HC) in %vol,ppm under equal conditions.
  • HC hydrocarbons
  • Fig. 3 shows the carbon monoxide value at increased idle (10 % according to ECE-standard 1997) under the same quantitative conditions, concerning the ratio additive to fuel.
  • a value of 0,05 %vol is measured. After adding the additive this value decreases to 0,01 %vol, which is a reduction of 80 %.
  • the hydrocarbon value, shown in Fig. 4 decreases from 20,14 %vol,ppm to 7,23 %vol,ppm at increased idle.
  • Fig. 5 The reduction of the emission of carbon particles with time of a diesel fuel engine, type AUDI diesel 5 cylinder, 140 hp (no oxidationkat) after the application of an additive, according to the present invention is shown in Fig. 5.
  • Said additive comprising 5,0 ml 1,1,2,2-tetraethoxyethane on 10,3 l diesel fuel, which is a ratio of additive to fuel of 1:2060, i. e. 0,485 ⁇ .
  • the value of emitted carbon particles decreases rapidly from 27,56 carbon particles m -1 to 3,78 carbon particles m -1 within 21 min, a reduction of 86,3 %.
  • After another 91 min the value reaches 0,82 carbon particles m -1 , which is a total reduction of emitted carbon particles of 97 %.
  • NOX emitted nitrogen oxides
  • acetals and hemiacetals of glyoxal are added to the fuel mixture.
  • Acetal formation is a well known process in organic chemistry and is described, e.g., in "Organic Chemistry", Morrison and Boyd, 2nd Ed., 0969, page 633 et seq., and is used to describe compounds of the general type RCH(OR') 2 .
  • RCH(OR') 2 acetaldehyde reacted with methanol in the presence of HCI yields acetaldehyde diethyl acetal (Acetal).
  • Such acetals and hemiacetals can be prepared according to the state-of-the-art as described above. A particular way to manufacture this products is described as follow: 660 grams of molecular sieves 4 ⁇ is placed in a column reactor. A mixture of 600 grams glyoxal trimer hydrated and 180 grams of amberlist 15 (ion-exchange resin) is filled on top of the molecular sieve in that column. The content of the column is heated up to 80°C. Then for example methanol or ethanol is pumped through the ion exchange resin as a catalyst and through the molecular sieve (water scavenger). The ratio of methanol to glyoxal is 4 mol, in the case of ethanol 12 mol.
  • the desired compound is obtained.
  • the purification and the separation of the desired compound from the solvent occurs by distillation. Methanol and ethanol are removed at 40°C and 22 torr. The purification occurs at 58°C and 20 torr.
  • the acetals and hemiacetals used in the present invention are obtained by the acetalization of glyoxal with linear and/or branched alcohols having C 1 -C 16 carbons such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, amylalcohol, with diols such as ethane diol, propane diol, butane diol, octane diol, neopentylglycol as well as triols such as glycerol. Furthermore mixtures of such mono-, di-, and trialcohols can be applied.
  • linear and/or branched alcohols having C 1 -C 16 carbons such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, amylalcohol
  • diols such as ethane diol, propane diol, butan
  • the acetals and hemiacetals used in the present invention can have various alkoxy groups at the -CH 2 -CH 2 -; unit of glyoxal.
  • different physical properties of the acetals and hemiacetals can be adjusted by the variation of the alkoxy groups.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Fats And Perfumes (AREA)
  • Treating Waste Gases (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP99948796A 1998-09-22 1999-09-20 Glyoxal as fuel additive Expired - Lifetime EP1124915B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19843380 1998-09-22
DE19843380A DE19843380A1 (de) 1998-09-22 1998-09-22 Glyoxal in wässriger Lösung als Additiv zur Schadstoffemissionssenkung bei fossilen Brennstoffen
PCT/EP1999/006949 WO2000017290A1 (en) 1998-09-22 1999-09-20 Glyoxal as fuel additive

Publications (2)

Publication Number Publication Date
EP1124915A1 EP1124915A1 (en) 2001-08-22
EP1124915B1 true EP1124915B1 (en) 2005-02-02

Family

ID=7881799

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Application Number Title Priority Date Filing Date
EP99948796A Expired - Lifetime EP1124915B1 (en) 1998-09-22 1999-09-20 Glyoxal as fuel additive

Country Status (19)

Country Link
EP (1) EP1124915B1 (pt)
JP (1) JP2002526595A (pt)
AT (1) ATE288467T1 (pt)
AU (1) AU755510B2 (pt)
BR (1) BR9914021A (pt)
CA (1) CA2345099A1 (pt)
DE (2) DE19843380A1 (pt)
DK (1) DK1124915T3 (pt)
EA (1) EA003932B1 (pt)
ES (1) ES2237156T3 (pt)
HU (1) HUP0103656A3 (pt)
IL (1) IL142067A0 (pt)
NO (1) NO20011331L (pt)
NZ (1) NZ510510A (pt)
PL (1) PL191757B1 (pt)
PT (1) PT1124915E (pt)
TR (1) TR200100839T2 (pt)
UA (1) UA72747C2 (pt)
WO (1) WO2000017290A1 (pt)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10116115A1 (de) * 2001-03-30 2002-10-10 Horst Kief Verfahren zur Reduktion der Schadstoffemission bei Verbrennungskraftmaschinen
FR2833607B1 (fr) * 2001-12-19 2005-02-04 Inst Francais Du Petrole Compositions de carburants diesel contenant des acetals de glycerol
FR2921385B1 (fr) 2007-09-21 2010-02-26 Inst Francais Du Petrole Procede de transformation de biomasse en produits renfermant des groupements acetals et leur utilisation comme biocarburants
EP2157157A1 (de) * 2008-08-19 2010-02-24 Thorsten Kief Verfahren zur Reduzierung der Schadstoffemission
RU2457238C1 (ru) * 2011-05-06 2012-07-27 Общество с ограниченной ответственностью "Интер-Октан" Унифицированный модификатор моторных топлив
EP3502215B8 (de) * 2017-12-21 2020-04-08 LAPIDE GmbH Reduktion der schadstoffemission von verbrennungsmotoren
AU2019446898A1 (en) * 2019-05-17 2021-11-25 Horst Kief Reduction of pollutant emissions of internal combustion engines

Family Cites Families (17)

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Publication number Priority date Publication date Assignee Title
US2655440A (en) * 1949-05-24 1953-10-13 California Research Corp Diesel fuel oil
US2560632A (en) * 1949-09-30 1951-07-17 Leonard Refineries Inc Stabilizing cracked distillate
NL112127C (pt) * 1957-10-11
GB891422A (en) * 1959-02-02 1962-03-14 Nobel Bozel Process for extracting sulphur dioxide from gas which contains it
NL250754A (pt) * 1959-04-24
DE2265593C2 (de) * 1971-05-05 1983-03-24 Österreichische Hiag-Werke AG, Wien Benzinzusatz aus Anilin, Acetalen und Alkoholen
DE2159975A1 (de) * 1971-12-03 1973-06-07 Veba Chemie Ag Glyoxalhalbacetale, verfahren zu ihrer herstellung und ihre verwendung
US4125382A (en) * 1977-04-11 1978-11-14 Basf Wyandotte Corporation Fuels containing polyoxyalkylene ether demulsifiers
JPS56159290A (en) * 1979-12-11 1981-12-08 Aeci Ltd Fuel and internal combustion engine operation
US4541837A (en) * 1979-12-11 1985-09-17 Aeci Limited Fuels
FR2544738B1 (fr) * 1983-04-21 1986-02-28 Inst Francais Du Petrole Nouveaux constituants de carburants pour moteurs automobile ou diesel
JP2792988B2 (ja) * 1990-02-09 1998-09-03 株式会社ジョモテクニカルリサーチセンター ディーゼルエンジン用燃料油
FR2700535B1 (fr) * 1993-01-19 1995-04-14 Hoechst France Procédé continu de fabrication industrielle du diméthoxyéthanal.
AU2692795A (en) * 1994-05-31 1995-12-21 William C. Orr Vapor phase combustion methods and compositions
JPH11509775A (ja) * 1995-07-27 1999-08-31 キーフ，ホルスト 自動車燃料用均一触媒の製造方法
DE19527423A1 (de) * 1995-07-27 1997-01-30 Horst Dr Med Kief Verfahren zur Herstellung von Homogenkatalysatoren bei Treibstoffen unter Verwendung von Ketonen
DE19702989A1 (de) * 1997-01-28 1998-07-30 Clariant Gmbh Umweltfreundlicher Dieseltreibstoff

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JP2002526595A (ja) 2002-08-20
IL142067A0 (en) 2002-03-10
HUP0103656A3 (en) 2004-06-28
PT1124915E (pt) 2005-06-30
EP1124915A1 (en) 2001-08-22
EA003932B1 (ru) 2003-10-30
DE69923575D1 (de) 2005-03-10
DE69923575T2 (de) 2006-03-23
BR9914021A (pt) 2001-07-03
NO20011331L (no) 2001-05-18
NZ510510A (en) 2002-12-20
CA2345099A1 (en) 2000-03-30
TR200100839T2 (tr) 2001-07-23
AU755510B2 (en) 2002-12-12
AU6192999A (en) 2000-04-10
HUP0103656A2 (hu) 2002-01-28
ES2237156T3 (es) 2005-07-16
DE19843380A1 (de) 2000-03-23
DK1124915T3 (da) 2005-06-06
WO2000017290A1 (en) 2000-03-30
PL191757B1 (pl) 2006-06-30
UA72747C2 (en) 2005-04-15
PL346755A1 (en) 2002-02-25
NO20011331D0 (no) 2001-03-16
ATE288467T1 (de) 2005-02-15
EA200100368A1 (ru) 2002-02-28

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