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
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Prior art keywords
glyoxal
fuel
additive
acetalization
gasoline
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EP99948796A
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German (de)
French (fr)
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EP1124915A1 (en
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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.

Abstract

Glyoxal in an aqueous solution is used in a fuel additive in order to reduce pollutants in the exhaust gases of gasoline and diesel engines. It is sufficient to add glyoxal in aqueous solution to gasoline in the dilution in the ratio of 1:1.000 to 1:20.000 and higher in order to obtain a reduction of unburned hydrocarbons and carbon monoxide in vehicles with catalytic converters at idle and at increased idle of almost 100 %. Esterified aliphats and polyethyleneglycol are added as emulsifiers and solubilizers. Additionally, glyoxal can be used in form of its acetals and hemiacetals with the resultant product being added to the fuel in combustion engines in order to reduce the pollutant emission and carbon particles/deposits.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention:
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.
2. Description of the Prior Art:
Fuels for the internal combustion engines and turbines damage the environment due to, among other factors, the incomplete combustion in the engines, of hydrocarbons, carbon monoxides and nitrogen oxides. 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. Also, 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.
The amelioration of fuel qualities by the addition of diverse substances is a familiar technique in the prior art. Thus, e.g., according to DE-PS 582 718, heavy metal salts, namely, copper, nickel, cobalt, zinc and chromium salts, as well as the condensation products of amines with compounds which contain one or more oxygen groups in addition to a carbonyl group, are added to the fuel in order to improve its knock resistance. In DE-PS 448 620 and DE-PS 455 525, fuels are described which have a content of iron carbonyl or nickel, cobalt and/or molybdenum carbonyl. However, these techniques have not become popular, because the use of metal carbonyls causes a metal oxide deposit in the combustion chamber of the vehicle and are toxic. 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. The following 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. 2,100,287; hydroquinone in a benzene solution from DE-PS 486 609; ether derivatives from DE-PS 703 030; alcohols from DE-PS 843 328; condensation products of alkylene oxides and alkylphenols from DE-PS 19 37 000; anthracene derivatives from Unites States Patent No. 1,885,190 and 1.4-dialkyl-arylamino-anthraquinone from EP 09 095 975 B1.
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. According to DE-PS 324 294, 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. According to 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.
The procedures described in the patents above are not commercialized. The described substances are partially toxic, carcinogenic or the procedures are too expensive. They do not add any value in the petrochemical market.
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.
Therefore, this literature describes to add acetone, which improves the solubility of the polyglyoxal but cannot prevent the polymerisation of glyoxal itself. On the other hand, acetone is not allowed in commercial fuels because of its low boiling point and resulting hazards.
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. As 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.
US 5,426,239 describes a process for the continuous preparation of dimethoxyethanal (DME) by reacting an aqueous solution of glyoxal with methanol. The literature just gives an improved process for producing this known material, which is described as "allowing access to products endowed with useful physiological or aromatic properties". No use of the compound as an addition to fuels is mentioned.
US 3,897,503 describes an improved process for pure glyoxal hemiacetals useful to produce acid-free glyoxal solutions by cleaving them hydrolytically into glyoxal hydrate and alcohol. No mentioning of fuel additives is to be found.
In DE 1144971 there is shown the use of leadtetraethyl in addition to monocarbonic acids, to achieve boosting of the octane number. In 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.
SUMMARY OF THE INVENTION
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.
In the present invention, 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. Preferably, different acetals and hemiacetals or a mixture thereof obtained by the acetalization of glyoxal are added to the fuel.
Additional objects, features and advantages will be apparent in the written description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1
is a graph of the reduction in emission of CO achieved through the use of the additives of the invention with the engine at idle;
Figure 2
is a similar graph of the reduction in emission of HC at idle;
Figure 3
is a similar graph of the reduction in emission of CO at increased idle;
Figure 4
is a similar graph of the reduction in emission of HC at increased idle;
Figure 5
is a graph of diesel emission of carbon particles with time showing the effects of the additives of the invention in reducing such emissions; and
Figure 6
is a graph of the reduction in emission of NOX with time showing the effects of the additives of the invention in reducing such emissions.
DETAILED DESCRIPTION OF THE INVENTION
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. In that process, 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. On one hand, this technique has the advantage that it is highly effective. On the other hand, however, 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.
In the present invention, 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. Here, glyoxal can be added to the fuel either together with flammable emulsifiers or in a chemical compound as described below. Compared to previous suggestions, 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. "Ecocool-ACC" of the firm Fuchs Öle) , as well as 10 milliliters polyethyleneglycol can easily be mixed with 500 milliliters gasoline. Here, after thorough mixing for some time, a slightly cloudy gasoline-additive-emulsion is obtained. If 10 milliliters methyltertiarybutylether are added hereto, the mixture becomes completely clear afterwards. It is, however, very important here that, first, the glyoxal in aqueous solution, the emulsifier and the polyethyleneglycol are very thoroughly homogeneously mixed and then, the mixture added to the gasoline. The gasoline-additive-emulsion obtained by this process is quite stable in storage. In high gasoline quantities, there is no longer any separation of phases. Aqueous glyoxal solution or concentrated glyoxal can also be added to "Aquazole" (trade name of ELF Aquitaine) as it is described in Focus 22/1999, page 188-189, Focus Magazin Verlag, Hamburg.
In the practice of the method of the invention, the addition of 500 milliliters of the gasoline-additive-emulsion to 40 liters gasoline has been found sufficient to obtain a reduction of unburned hydrocarbons of 95% in vehicles with catalytic converters at increased idle and at idle after the cars have been driven five kilometers in urban driving. Usually, carbon monoxide can no longer be identified under these conditions. Also a reduction of the emission of nitrogen oxides (NOX) of approximately 90 % has been obtained.
The tables that follow provide the results of a statistical survey on the results of tests with gasoline to which the above-described additive was added. As only 4 grams glyoxal were mixed into 40 liters of gasoline, it can be calculated that glyoxal shows its effectiveness as a homogeneous catalyst at the ppm-level. Furthermore, the quantity of water of 10 milliliters per 40 liter gasoline is so low that there is no danger of corrosion for the engine. Any and all components of the described additive are flammable and nontoxic so that toxic side effects can be excluded.
In diesel fuel, the aqueous glyoxal solution as described above is even more easily soluble than in gasoline. Here, 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%.
Tables I and II below as well as the graphs shown in Figures 1-5 provide the results of emissions tests using the glyoxal solution additive of the invention:
Reduction in emission through glyoxal emulsion in gasoline (at idle) n=22
Date CO before % vol CO after % vol HC before % vol, ppm HC after %vol, ppm
07.03.1998 0,01 0 34 5
07.03.1998 0 0 34 5
07.03.1998 0,01 0 79 2
07.03.1998 0 0 8 7
06.26.1998 0,01 0 6 3
06.26.1998 0 0 21 10
06.26.1998 0 0 5 7
06.26.1998 0 0 6 9
05.22.1998 0 0 5 3
05.22.1998 0 0 9 3
05.22.1998 0,02 0 54 10
05.22.1998 0,02 0,01 20 11
04.08.1998 0.1 0 111 6
03.25.1998 0 0 22 29
03.25.1998 0 0 6 4
03.23.1998 0 0 6 2
03.23.1998 0,01 0 16 0
03.23.1998 0 0 4 4
03.18.1998 0,07 0,09 34 13
03.05.1998 0,04 0 42 1
03.05.1998 0,04 0 57 7
without date 0,02 0,01 15 9
average value 0,02 0,01 27,00 6,82
standard deviation 0,03 0,02 27,67 6,06
Reduction in emission through glyoxal emission in gasoline (at increased idle) n=22
Date CO before % vol CO after % vol HC before %vol, ppm HC after % vol, ppm
07.03.1998 0,26 0 99 9
07.03.1998 0,02 0 56 5
07.03.1998 0,06 0 27 5
07.03.1998 0 0 14 11
06.26.1998 0 0 5 2
06.24.1998 0 0 10 12
06.24.1998 0 0,1 10 15
06.24.1998 0,03 0,01 8 9
05.22.1998 0 0 5 2
05.22.1998 0 0 12 2
05.22.1998 0,03 0 13 7
05.05.1998 0 0 10 12
04.08.1998 0,12 0 41 6
03.25.1998 0,03 0,01 17 13
03.25.1998 0,01 0,02 8 5
03.23.1998 0 0 8 5
03.23.1998 0,1 0 27 0
03.23.1998 0 0 11 6
03.18.1998 0,29 0,05 13 17
03.05.1998 0,13 0 24 3
03.05.1998 0,01 0 16 8
without date 0,05 0,04 9 5
average value 0,05 0,01 20,14 7,23
standard deviation 0,08 0,02 21,49 4,56
Conditions:
All cars were BMW Type 5 (525 or 528)
measuring equipment:
Digas AVL Type 465 (Graz, Austria)
Sensor AVL Type 1554
The Figures 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. After application of an 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. Here after the application of the additive a reduction of nearly 75 % from 27,00 %vol,ppm to 6,82 %vol,ppm is obtained.
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. With conventional gasoline 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 %. Also the hydrocarbon value, shown in Fig. 4, decreases from 20,14 %vol,ppm to 7,23 %vol,ppm at increased idle.
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 ‰. After adding the additive 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 %.
Finally Fig. 6 shows the reduction of emitted nitrogen oxides (NOX) in %vol,ppm with time in the exhaust gas of an gasoline engine, type Ford Van V6 (1996), at increased idle with 1300 to 1370 RPM. Without the additive according to the invention a value of 340 %vol,ppm is measured. After the application of 0,86 ‰ (= 50,0 ml) 1,1,2,2-tetramethoxyethane (TME) the value decreases after approximately 25 min to 135 %vol,ppm and after another 15 min the value drops to 37 %vol,ppm, which is a overall reduction of nearly 90 %.
In an especially preferred embodiment of the present invention, instead of glyoxal in aqueous solution, 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. For example, in simplest terms, acetaldehyde reacted with methanol in the presence of HCI yields acetaldehyde diethyl acetal (Acetal). Similarly, alcohols will be added to aldehydes to produce "hemiacetals" in a reaction catalyzed by both acids and bases. A hemiacetal in the presence of an alcohol and an acid catalyst is converted to an acetal. See also, "Organic Chemistry", Holt, Rinehart and Winston, 1964, pages 308-310.
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 Å 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.
During 16 hours 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 C1-C16 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. Thus, the acetals and hemiacetals used in the present invention can have various alkoxy groups at the -CH2-CH2-; unit of glyoxal. Thus different physical properties of the acetals and hemiacetals can be adjusted by the variation of the alkoxy groups.
While the invention has been shown in only two of its forms, it is not thus limited but is susceptible to various changes and modifications without departing from the spirit thereof.

Claims (10)

  1. A method for reducing pollutant emission of mineral oil fuels in internal combustion engines, the method comprising the step of:
    forming a fuel additive comprising an aqueous solution of glyoxal and emulsifiers and/or tensids and/or antifreeze agents;
    adding the aqueous solution of glyoxal to a hydrocarbon fuel or forming a fuel additive comprising an acetal and/or hemiacetal of glyoxal, the glyoxal being bound by acetalization with alcohols and/or diols and/or triols in an aqueous phase; separating the resulting product from its aqueous phase and thereafter adding the product to a hydrocarbon fuel wherein the ratio of the fuel additive to fuel is between 1 : 1.000 and 1 : 20.000
    said fuel being supplied to the internal combustion engine.
  2. The method of claim 1, wherein the emulsifiers are esterified aliphats and/or polyethyleneglycol and/or tensids and the antifreeze agents are methanol, glycerol, glycol.
  3. The method of claim 2, wherein the ratio of glyoxal solution, esterified aliphats and/or polyethyleneglycol is 2 : 1 : 1. in the fuel additive.
  4. The method of claim 3, further comprising the steps of:
    first mixing part of the fuel with the glyoxal-emulsifier-mixture; and thereafter adding methyl-tertiary-butylether in a ratio of 1 : 50 to 1 : 100.
  5. The method of claim 1, wherein the acetalization of the glyoxal is achieved by reacting the glyoxal with a second reactant selected from the group consisting of linear and branched alcohols from C1 to C16 and/or linear and/or branched diols and/or trials from C1 to C16, the acetalization agent being especially selected from the group of consisting of methanol, ethanol, isopropanol, tertiary butanol, 1,3-propandiol, neopentylglycol and glycerol.
  6. The method of claim 5, wherein a mixture of glyoxal and/or different acetals and/or hemiacetals obtained by acetalization of glyoxal is added to the fuel.
  7. A hydrocarbon fuel for internal combustion devices in vehicles and fuel fired heating plants, comprising a mineral oil fuel and a fuel additive comprising a) an aqueous solution of glyoxal and emulsifiers and/or tensides and/or antifreeze agents or b) an acetal of glyoxal and/or hemiacetal of glyoxal wherein the ratio of the fuel additive to fuel is between 1 : 1.000 and 1 : 20.000 in case of gasoline and below 1 : 5.000 to 1 : 20.000 in case of diesel oil.
  8. The fuel according to claim 7, wherein the emulsifiers are esterified aliphats and/or polyethylenglycol and/or tensides and the antifreeze agents are methanol, glycerol and glycol.
  9. The fuel according to claim 8, wherein the ration of glyoxal solution, esterified aliphats and/or potyethytenglycol is essentially 2 : 1 : 1.
  10. The fuel according to one of claims 7 to 9, wherein said acetals and/or semiacetals comprising C1-C16-alkoxy groups, said acetals and/or hemiacetals preferential are obtained by acetalization of glyoxal with linear and/or branched mono-, di- and trialcohols having C1-C16 carbons, said mono-, di- and trialcohols preferentially are selected from the group consisting of methanol, ethanol, isopropanol, tertiary, butanol, 1,3-propandiol, neopentylglycol and glycerol.
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 (en) 1998-09-22 1998-09-22 Process for reducing the pollutant emissions from I.C. engines comprises adding glyoxal in an aqueous solution to the fuel
PCT/EP1999/006949 WO2000017290A1 (en) 1998-09-22 1999-09-20 Glyoxal as fuel additive

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DE10116115A1 (en) * 2001-03-30 2002-10-10 Horst Kief Process for reducing pollutant emissions in internal combustion engines
FR2833607B1 (en) * 2001-12-19 2005-02-04 Inst Francais Du Petrole DIESEL FUEL COMPOSITIONS CONTAINING GLYCEROL ACETALS
FR2921385B1 (en) * 2007-09-21 2010-02-26 Inst Francais Du Petrole PROCESS FOR TRANSFORMING BIOMASS TO PRODUCTS COMPRISING ACETAL GROUPS AND THEIR USE AS BIOFUELS
EP2157157A1 (en) * 2008-08-19 2010-02-24 Thorsten Kief Method for reducing pollutant emissions
RU2457238C1 (en) * 2011-05-06 2012-07-27 Общество с ограниченной ответственностью "Интер-Октан" Universal engine fuel modifier
PL3502215T3 (en) * 2017-12-21 2020-07-27 Lapide Gmbh Reduction of pollutant emissions from combustion engines
US20220251463A1 (en) * 2019-05-17 2022-08-11 Thorsten Kief Reduction of pollutant emissions of internal combustion engines

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