EP0904337A1 - Additifs pour carburants - Google Patents

Additifs pour carburants

Info

Publication number
EP0904337A1
EP0904337A1 EP97918251A EP97918251A EP0904337A1 EP 0904337 A1 EP0904337 A1 EP 0904337A1 EP 97918251 A EP97918251 A EP 97918251A EP 97918251 A EP97918251 A EP 97918251A EP 0904337 A1 EP0904337 A1 EP 0904337A1
Authority
EP
European Patent Office
Prior art keywords
fuel
organo
group
metals
fuel additive
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.)
Withdrawn
Application number
EP97918251A
Other languages
German (de)
English (en)
Inventor
Donald Barr
Stephen Leonard Cook
Paul Joseph Richards
Maurice William Rush
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.)
Innospec Ltd
Original Assignee
Associated Octel Co Ltd
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
Priority claimed from PCT/GB1996/000990 external-priority patent/WO1996034074A1/fr
Application filed by Associated Octel Co Ltd filed Critical Associated Octel Co Ltd
Publication of EP0904337A1 publication Critical patent/EP0904337A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/1814—Chelates
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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
    • F02B51/00—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines
    • F02B51/02—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines involving catalysts
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1828—Salts thereof
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a process for improving the combustion of fuel and/or improving the oxidation of carbonaceous products derived from the combustion or pyrolysis of fuel.
  • the invention further relates to fuel additives suitable for use in such a process.
  • Products from the combustion or pyrolysis of hydrocarbon fuels include carbon monoxide, nitrous oxides (N0 X ) , unburnt hydrocarbons and particulates.
  • These particulates include not only those particulates which are visible as smoke emission, but also unburned and partially oxidised hydrocarbons from fuel and the lubricants used in engines.
  • the particulate and soot emission are known to be harmful and themselves contain harmful pollutants.
  • unburned or partially oxidised hydrocarbons emitted to the atmosphere are irritant astringent materials.
  • Diesel fuels and diesel engines, and fuel combustors for heating units, are particularly prone to the emission of small size soot particulate material in the exhaust gas.
  • Diesel engines especially are prone to emission of high levels of particulate matter when the engine is overloaded, worn or badly maintained. Particulate matter is also emitted from diesel engines exhausts when engines are operated at partial load and these emissions are normally invisible to the naked eye.
  • Combustors fuelled by liquid hydrocarbon fuels are also prone to emission of unburned and partially burned substances especially when operated on a frequent start- stop programme or when the burner parts are inadequately maintained. As energy regulations become more stringent the control and stop start operation of combustors must be improved.
  • E.G.R. Exhaust Gas Recirculation
  • exhaust gas recycled in a controlled way to the intake of a diesel exhaust can contribute to the reduction of certain emissions species, mainly oxides of nitrogen.
  • soot particles in the exhaust gas also become recirculated within the engine.
  • Particulate traps having the capability to oxidise collected material are also proposed in the light of forthcoming legislation. Such devices are well known to those familiar with the art and some examples are discussed in "Advanced techniques for thermal and catalytic diesel particulate trap regeneration", SAE International Congress (February 1985) SAE Special
  • low speed engine operation can cause carbonaceous deposits to form on the active parts of the diesel engine oxidation catalyst and so inhibit the effectiveness of the catalyst until a sufficiently high enough gas temperature is available to regenerate the catalyst active surface.
  • Exhaust catalyst devices fitted to diesel and gasoline fuelled engines become effective after engine start up when the exhaust gas passing the catalyst substrate exceeds about 250 C. Experimental work is proceeding to develop catalyst systems effective from temperatures below this level. Details are given in the proceedings of the S.A.E. International Congress February 1995; S.A.E. publications 950404 to 950412, inclusive.
  • Cold engine operation such as stop start driving in gasoline vehicles, or prolonged engine idling for diesel engines, can cause a layer of soot and other carbonaceous material to form over the active catalyst surfaces.
  • Two stroke engines are also prone to the formation of deposits in the combustion chamber, such as on the piston crown and around the piston rings and ring grooves. Deposits also form in the exhaust ports of two stroke engines causing a loss of engine performance efficiency and emission control.
  • WO-A-94/11467 to Platinum Plus discloses the use of platinum compounds in conjunction with a trap to lower the unburned hydrocarbon and carbon monoxide concentration of diesel exhaust gases. Lithium and sodium compounds are also claimed to be useful in lowering the regeneration temperature of the trap.
  • EP-A-207 560 to Shell concerns the use of succinic acid derivatives and their alkali or alkaline earth metal (especially potassium) salts as additives for increasing the flame speed within spark ignition internal combustion engines.
  • EP-A-555 006 to Slovnaft AS discloses the use of alkali or alkaline earth metal salts of derivatised alkenyl succinates as additives for reducing the extent of valve seat recession in gasoline engines designed for leaded fuel but used with non-leaded.
  • GB-A-2 248 068 to Exxon teaches the use of additives containing an alkali, an alkaline earth and a transition metal to reduce smoke and particulate emissions during the combustion of diesel fuel.
  • EP-A-0 476 196 to Ethyl Petroleum Additives teaches the use of a three part composition including a soluble and stable manganese salt, a fuel soluble and stable alkali or alkaline earth metal and a neutral or basic detergent salt to reduce soot levels, particulates, and the acidity of carbonaceous combustion products.
  • EP-A-0 423 744 teaches the use of a hydrocarbon soluble alkali or alkaline earth metal containing composition in the prevention of valve seat recession in gasoline engines designed for leaded but run on unleaded fuel.
  • the present invention thus provides a process of improving the combustion of fuel and/or improving the oxidation of carbonaceous products derived from the combustion or pyrolysis of fuel (such as with the use of a particulate trap used with diesel engines) , the process comprising adding to the fuel before the combustion thereof a composition comprising a mixture of two or more organo-metallic complexes of Group I metals.
  • the composition comprises a mixture of two identical or different organometallic complexes of different Group I metals .
  • the invention provides the use of a combination of organo-metallic complexes as hereinbefore defined for improving combustion of fuel and/or improving the oxidation of carbonaceous products derived from the combustion or pyrolysis of fuel (such as with the use of a particulate trap for use with diesel engines) , wherein the complexes are added to the fuel before the combustion thereof, preferably wherein the total concentration of the metals of the Group I organo-metallic complexes in the fuel before combustion is 100 ppm or less, preferably 50 ppm or less, more preferably 30ppm or less.
  • the invention provides a fuel additive comprising a mixture of two or more organo-metallic complexes of Group I metals, together with a fuel-soluble carrier liquid miscible in all proportions with the fuel.
  • Concentrations of the organo-metallic complexes in the additive composition may range from 10 to 90% by weight. As high a concentration as may practically be achieved is preferred. Practical considerations include solubility of the complex and in particular the viscosity of the resulting concentrate. Compositions containing from 40 to 60% by weight of organo-metallic complexes are often preferred as typically offering a good compromise between concentration and viscosity.
  • Suitable organic carriers for the formulations include aromatic hydrocarbon solvent fractions such as Shellsol ABTM, Shellsol RTM and Solvesso 150TM. De- aromatised solvent fractions such as Shellsol D70 are also suitable. Other suitable carrier liquids miscible with diesel and other similar hydrocarbon fuels will be apparent to those skilled in the art.
  • particulate traps are known to those skilled in the art including as non-limiting examples 'cracked wall' and 'deep bed' ceramic types and sintered metal types.
  • the invention is suitable for use with all particulate traps; the optimum dose rate is a function of the trap type.
  • a particulate filter trap of the 'cracked wall' type such as the Corning
  • a preferred total concentration of the metals of the Group I organometallic complexes in the fuel is 100 ppm or less, preferably 20ppm or less.
  • a particulate filter trap of the 'deep bed' type such as
  • a preferred total concentration of the metals of the Group I organo ⁇ metallic complexes in the fuel is 50 ppm or less, preferably 20ppm or less, e.g. 5ppm or less.
  • the key advantages of the present invention are that it provides additives for diesel and other hydrocarbon fuels that give an overall emissions benefit to the environment on combustion by any one or more of: improving the combustion process,- controlling the formation of soot and carbonaceous deposits in engines and combustors; and improving the oxidation of particulates within trap systems, engines or exhaust systems.
  • the composition of the present invention promotes and sustains combustion in the trap.
  • Another key advantage is that the composition of the present invention may be used in low dosage amounts. Whilst any combination of two or more alkali metals may be used, combinations of potassium and sodium are particularly preferred. This is on the grounds of their low toxicity, low cost and the ready availability of sources of these metals compared to the other alkali metals lithium, rubidium and cesium.
  • Preferred organometallic complexes of potassium and sodium are those which may readily be prepared from an inexpensive salt of the metal, such as the hydroxide or oxide.
  • each organo-metallic complex is fuel soluble.
  • each organometallic complex is soluble in a fuel-compatible solvent such that each organometallic complex is soluble to the extent of 10 wt%, preferably 25 wt% and most preferably 50 wt% or more in the solvent.
  • the fuel-compatible solvent may comprise a poly(butene) .
  • the ratio of these is preferably in the range of from 20:1 to 1:20, e.g. from 10:1 to 1:10. More preferably, the ratio of these is in the range of from
  • the two complexes are of sodium and potassium, these are advantageously added such that the ratio by weight of sodium to potassium is in th range of from 20:1 to 2:1, more preferably from 10:1 t :1.
  • each of th rgano-metallic complexes is of the formula M(R) m .nL wi ⁇ _re M is the cation of an alkali metal of valency m;
  • R is the residue of an organic compound RH, where R is an organic group containing an active hydrogen atom H replaceable by the metal M and attached to an O, S, P, N or C atom in the group R;
  • n is a positive number indicating the number of donor ligand molecules forming a bond with the metal cation, but which can be zero;
  • L is a species or functional group capable of acting as a Lewis base.
  • the term "species capable of acting as a Lewis base” includes any atom or molecule that has one or more available electron pairs in accordance with the Lewis acid-base theory.
  • R and L for at least one of the complexes are in the same molecule.
  • Each organometallic complex may be dosed to the fuel at any stage in the fuel supply chain.
  • each complex is added to the fuel close to the engine or combustion systems, withm the fuel storage system for the engine or combustor, at the refinery, distribution terminal or at any other stage in the fuel supply chain.
  • fuel includes any hydrocarbon that can be used to generate power or heat.
  • fuel also covers fuel containing other additives such as dyes, cetane improvers, rust inhibitors, antistatic agents, antioxidants, reodorants, gum inhibitors, metal deactivators, de-emulsiflers, upper cylinder lubricants, and anti-icing agents.
  • other additives such as dyes, cetane improvers, rust inhibitors, antistatic agents, antioxidants, reodorants, gum inhibitors, metal deactivators, de-emulsiflers, upper cylinder lubricants, and anti-icing agents.
  • the term covers diesel fuel.
  • diesel fuel means a distillate hydrocarbon fuel or for compression ignition internal combustion engines meeting the standards set by BS 2869 Parts 1 and 2 as well as fuels in which hydrocarbons constitute a manor component and alternative fuels such as rape seed oil and rape oil methyl ester.
  • the combustion of the fuel can occur in, for example, an engine such as a diesel engine, or any other suitable combustion system.
  • suitable combustion systems include recirculation engine systems, domestic burners and industrial burners
  • the present invention therefore relates to additives for liquid hydrocarbon fuel, and fuel compositions containing them.
  • composition of the present invention can have many uses, some of which are now described.
  • the composition of the present invention achieves a useful level of particulates suppression and to such an extent that it decouples this trade off, thereby giving the engineer more freedom to achieve power output or fuel economy within a given emission standard.
  • the composition of the present invention may be effective in reducing engine out emissions or as a combustion catalyst aiding the oxidation of trapped particles. Either way, the composition of the present invention provides for simpler, safer and less costly traps by enabling less frequent, less intense or less energetic regeneration, whether the heat required for the regeneration is provided by the exhaust gas or through some external mechanism.
  • the combustion of fuel containing the composition of the present invention enables engines to be run at a full load and at a fractional load with a suitable trap arrangement and in doing so a self regenerating mechanism is initiated.
  • a fuel containing the composition of the present invention there are provided two broad modes of trap function. First, a soot and particulate trapping stage associated with a minor clogging function can be observed. This is then followed by an automatic burn off or self-regeneration function. Trap conditions which favour self regeneration are influenced by particulate size and formation, the composition of unburned hydrocarbons, the back pressure and composition of the exhaust gas in the exhaust system. These discrete functions of trapping then burn off are particularly recordable at light to medium engine duty.
  • the composition of the present invention can significantly reduce or eliminate the need for regeneration initiation and control devices.
  • the need for energy input to initiate the regeneration can also be substantially reduced or eliminated for many engine designs.
  • the trapping and regeneration mechanisms operate simultaneously giving excellent control of the particulate emissions from diesel exhaust.
  • the composition of the present invention is designed to remain compatible with hydrocarbon fuels and remain stable up to the point of entry to the combustion zone.
  • the composition of the present invention when burned with the fuel can reduce the soot and carbonaceous material entrained in the exhaust gas recycle system of certain engines.
  • the levels of soot and carbonaceous material that are subsequently trapped in the engine becomes reduced.
  • Burning of a fuel comprising the composition of the present invention gives particulate matter remaining in the exhaust gas which is in a form readily collectable on a trap. Further, when the fuel is burned with the additive of the present invention the trapped material exhibits a reduced ignition temperature and oxidation of the trapped material is enhanced, when compared to that of fuel burned without the composition of the present invention. The burning of soot and other hydrocarbons from the surfaces of a trap therefore provides a way to regenerate the filter and so prevent the unacceptable clogging of particulate traps.
  • the term "regeneration” or “regenerating” means cleaning a particulate trap so that it contains minimal or no particulates.
  • the usual regeneration process includes burning off the trapped particulates in and on the particulate trap.
  • Regeneration of the trap is accompanied by a reduction in pressure drop across the trap.
  • the synergistic combination of two alkali metals offers a number of advantages. Firstly, the regeneration of the trap may be enhanced such that there is a lower average back pressure across the trap. Secondly, regeneration of the trap may be caused to occur with greater reliability and frequency, such that there is a less extreme variation in back pressure across the trap. This can be detected e.g. by logging trap back pressure at regular discrete intervals whilst running the engine under steady conditions and determining the standard deviation as well as the mean of the back pressure readings.
  • the composition of the present invention is designed so that very low levels of combustion or pyrolysis ash are formed. In this way clogging of the trap from additive residue is kept to a minimum.
  • the fuel may cause the carbonaceous deposits that form during stop start driving on the active surfaces of catalytic converters to be cleared away even from low driving duty thereby enabling a fast light off or early regeneration to full conversion efficiency.
  • the fuel When a fuel comprising the composition of the present invention is burned the fuel provides a significant reduction in levels of soot and carbonaceous deposits that form on the combustion surfaces of engines in the piston rings and piston ring bands, and also in the exhaust ports, thereby contributing to a maintenance of engine performance emissions and longevity.
  • the composition of the present invention is designed such that the soot and hydrocarbons burned become emitted as water vapour, carbon monoxide and carbon dioxide.
  • the composition of the present invention provides ultimate products that are readily water soluble, or soluble in solvents non- corrosive towards exhaust system components thereby simplifying any recycle of the system.
  • composition of the present invention is fuel-soluble or fuel miscible. This serves to reduce the complexity and cost of any on-board dosing device.
  • a further advantage of a highly preferred composition of the invention is that it can be supplied in concentrated form in a suitable solvent that is fully compatible with diesel and other hydrocarbon fuels, such that blending of fuel and additive may be more easily and readily carried out.
  • a further advantage of a highly preferred composition of the present invention is that it is at least resistant and preferably totally inert towards water leaching, thus providing a fuel additive that is compatible with the fuel handling, storage and delivery systems in common use.
  • diesel fuel often encounters water, especially during delivery to the point of sale and so the composition of the present invention is not affected by the presence of that water.
  • the alkali metal complexes have the general formula
  • R is the residue of an organic compound of formula RH where H represents an active hydrogen atom reactive with the metal M and attached either to a hetero atom selected from O, S and N in the organic group R, or to a carbon atom, that hetero or carbon being situated in the organic group R close to an electron withdrawing group, e.g. a hetero atom or group consisting of or containing 0, S or N, or aromatic ring, e.g.
  • n is a number indicating the number of organic electron donor molecules (Lewis bases) forming dative bonds with the metal cation in the complex, usually up to five in number, more usually an integer from 1 to 4, and L is one or more organic electron donor ligands (Lewis base) .
  • R and L may be combined in the one molecule, in which case n can be and often is zero and L is a functional group capable of acting as a Lewis base.
  • the Lewis base metallo- organic co-ordination complexes used in accordance with the present invention contain the residue of an organic molecule RH which contains an active hydrogen atom H which is replaceable with a metal cation.
  • the active hydrogen atom will be attached to a hetero atom (O, S, or N) or to a carbon atom close to an electron withdrawing group.
  • the electron withdrawing group is a hetero atom or group
  • the hetero atom or group may be situated in either an aliphatic or alicyclic group, which, when the active hydrogen group is an >NH group, may or may not, but usually will contain that group as part of a heterocyclic ring.
  • Suitable complexes are derived from a ⁇ -diketone of the formula R 1 C(0)CH 2 C(0)R 2
  • R 1 or R 2 is C,-C 5 , alkyl or substituted alkyl, e.g. halo-, amino-, alkoxy- or hydroxyalkyl-, C 3 -C 6 cycloalkyl, benzyl, phenyl or Cj-C 5 alkylphenyl, e.g. tolyl, xylyl, etc., and where R 1 may be the same as or may be different to R 2 .
  • Suitable ⁇ -diketones include: hexafluoroacetylacetone: CF 3 C(0)CH 2 C(0)CF 3 (HFA) ; 2,2,6,6-tetramethylheptane-3,5-dione: (CH 3 ) 3 CC(0)CH 2 C(0)C(CH 3 ) 3 .
  • suitable compounds include phenolic compounds containing from 6-30 carbon atoms, preferably substituted phenols containing from 1- 3 substituents selected from alkyl, alkylaminoalkyl, and alkoxy groups of 1-8 carbon atoms, e.g. cresols, guiacols, di-t-butylcresols, dimethylaminomethylene- cresol.
  • the substituted phenols are particularly preferred.
  • Especially preferred compounds wherein the hydrogen atom is attached to oxygen in the organic compound RH are those derived from reaction of a metal hydroxide or other alkali metal source with an alkyl or alkenyl substituted succinic anhydride or the hydrolysis product.
  • anhydrides are those prepared by reaction of oligomerised isobutenes or other simple olefins with maleic anhydride.
  • a wide variety of such alkyl or alkenyl substituted succinic anhydrides and a range of techniques for their preparation are known to those skilled in the art.
  • a high molecular weight poly(isobutene) substituent provides the resulting complex with good hydrocarbon solubility at the cost of lower metal content.
  • Suitable compounds are succinimide, 2-mercaptobenzoxazole, 2-mercapto- pyrimidine, 2-mercaptothiazoline, 2- mercaptobenzimidazole, 2-oxobenzoxazole.
  • L can be any suitable organic electron donor molecule (Lewis base) , the preferred ones being hexamethylphosphoramide (HMPA) , tetramethylethylenediamine (TMEDA) , pentamethyldiethylenetriamine, dimethylpropyleneurea (DMPU) , dimethylimidazolidinone (DMI) , dimethylcarbonate (DMC) , dimethylsulphoxide (DMSO) , dimethylformamide (DMF) .
  • HMPA hexamethylphosphoramide
  • TEDA tetramethylethylenediamine
  • DMPU dimethylpropyleneurea
  • DMC dimethylimidazolidinone
  • DMC dimethylcarbonate
  • DMSO dimethylsulphoxide
  • DMF dimethylformamide
  • L is a functional group capable of acting as a Lewis base donor, preferred ones being dimethylaminomethyl (-CH 2 N(CH 3 ) 2 ) , ethyleneoxy(-OCH 2 CH 2 0-) , ethyleneamine (-N(R)CH 2 CH 2 N(R) -) , carboxy( -C0 2 H) and ester (-C0 2 CH 2 R) .
  • n 1, 2, 3, or 4.
  • R comprises L
  • n can be and often is zero.
  • organometallic compounds described may be added directly to the fuel, either external to the vehicle or by using an on board dosing system, they will preferably first be formulated as a fuel additive composition or concentrate containing the substance, or mixtures thereof possibly along with other additives, such as detergents, anti foams, dyes, cetane improvers, corrosion inhibitors, gum inhibitors, metal deactivators, de-emulsiflers, upper cylinder lubricants, anti-icing agents, etc., in an organic carrier miscible
  • organo-metallic complex it is desirable to have a high concentration of organo-metallic complex present in the fuel additive composition.
  • concentration of organo-metallic complex may range from 10 to 90% by weight.
  • compositions containing from 40 to 60% by weight of organo-metallic complex are preferred.
  • composition of the present invention reduces the ignition temperature and/or promotes oxidation of particulate matter.
  • soot formation and decay there are four basic mechanisms to explain soot formation and decay. These are: mass growth, coagulation, pyrolysis and oxidation.
  • metallic additives appear to work by enhancing oxidation rather than reducing soot formation.
  • Alkali metals, particularly metal oxides thereof, have been shown to be effective in rich pre-mixed flame studies. Suggested mechanisms for alkali metals include a charge transfer process which limits coagulation, especially in the combustion space of a diesel engine cylinder, thus promoting soot burn out and limiting the formation of larger more stable soot particles.
  • a particular advantage of the complexes of this invention is their low nuclearity, many being monomeric in character, although some are dimeric and trimeric, tetrameric or higher.
  • This low nuclearity means that, in contrast to overbased metal soaps (i.e. the traditional method of providing oil-soluble metal compounds) the complexes used in accordance with the present invention provide a uniform distribution of metal atoms throughout the fuel, each metal atom theoretically being available to enhance combustion of particulates both within the engine and exhaust system and in traps.
  • the overbased metal soaps essentially consist of individual micelles containing a number of metal (e.g.
  • alkali or alkaline earth metal alkali or alkaline earth metal
  • inorganic anions typically carbonate
  • the metal will not be uniformly dispersed throughout the fuel as individual atoms, but in clusters, or micelles. Further, only a limited number of metal atoms are available on the surface of the micelle for action, so the effectiveness of those soaps is low. Also, since the soaps are non ⁇ volatile there is a significant risk of increased deposit formation in the engine itself and in the fuel injectors, including the fuel injectors of oil fire boilers etc.
  • composition of the present invention is also attributable to its volatility as the combustion process is a vapour phase reaction, essentially requiring the particulate suppressant to be volatile in order to have an effect.
  • Figure 1 indicates the pressure drop across a 'cracked wall' trap with time on combustion of a fuel in accordance with the invention.
  • Figure 2 indicates the effect of Na:K ratio on mean exhaust gas pressure.
  • Figure 3 indicates the effect of Na:K ratio on exhaust gas pressure (mean + 2 standard deviations) .
  • Example 1 Preparation of 1,3-dimethylimidazolidinone adduct of sodium 2,2, 6,6-tetramethylheptane-3,5-dionate: [Na(TMHD) .DMI]
  • Example 2 Preparation of sodium salt of poly(isobutenyl) succinic acid, approx. 1,000 molecular weight [Na(PIBSA 1000 ) ]
  • PIBSA poly(isobutenyl) succinic anhydride
  • Potassium hydride (KH, 0.90 g, 22.5 mmol) was washed of mineral oil, dried and placed in a Schlenk tube. Hexane was then added followed by DMI (7 ml, 64.22 mmol) . Some effervescence occurred, implying reaction or dissolution, and a green coloration was apparent. TMHD (4.4 ml, 21.05 mmol) was then added slowly, as a very vigorous reaction takes place. After about fifteen minutes the reaction subsided and an oil settled out of solution. The two-phase liquid was cooled in an ice-box (to -10°C) and a solid crystalline mass formed from the oil part over about half an hour.
  • Example 5 Dimethylimidazolidinone adduct of potassium 2, 6-ditertiarybutyl-4-methyl phenol, [K(BHT) .2DMI] .
  • Example 6 Dimethylimidazolidinone adduct of sodium 2,6' ditertiarybutyl-4-methyl phenol, [Na(BHT) .3DMI] .
  • example 3 The method of example 3 is used, with the appropriate change in Lewis base and Lewis base:metal ratio.
  • the adduct is sufficiently soluble in toluene to permit recrystallisation.
  • the crystals obtained have melting point 96-98°C.
  • Example 7 Dimethylimidazolidinone adduct of sodium 2- methoxy phenol, [Na(TMP) .DMI] .
  • example 4 The method of example 4 is used, with the appropriate change in Lewis base:metal ratio.
  • the adduct is sufficiently soluble in toluene to permit recrystallisation.
  • the crystals obtained have melting point 87-89°C.
  • Example 8 Preparation of the sodium salt of molecular weight 420 poly(isobutenyl)succinic anhydride.
  • the reactor was carefully washed and the washings analysed for sodium.
  • mass balance the NaPIBSA 420 solution was expected to contain 2.37 wt% Na, it was found to contain 2.13% by analysis.
  • Example 9 Preparation of No. Average Molecular Weight 420 Poly(isobutylene) Succinic Anhydride - PIBSA 420 .
  • a reactor was charged with BP-Hyvis XD-35 poly(isobutylene) (12.906 kg, 40.33 mol) and heated to 100°C with stirring before adding maleic anhydride (5.966 kg, 60.88 mol) .
  • the temperature of the oil bath supplying the reactor jacket was set to 220°C, the internal reactor temperature reached 185°C after three hours. This was taken as the start of the reaction time.
  • the oil bath temperature was lowered to 212°C and the reaction mix stirred during some 30 hours. At the end of this period a vacuum was applied and the excess maleic anhydride distilled out. After 15 hours under vacuum, residual maleic anhydride content was 0.0194 wt% and residual PIB 19.9 wt% . Some 13.888 kg of brown, viscous material was recovered.
  • Example 10 Preparation of Potassium Salt of PIBSA 420 .
  • TNI Solveso 150 (462.53 g) .
  • the contents were warmed to 50°C and stirred until homogenous.
  • KOH flake 47.88 g, 0.77 mol if 10% H 2 0
  • the solids dissolved and FTIR analysis showed an absence of the 1863 cm "1 absorption due to the PIBSA.
  • the solution was analysed by AAS as containing 3.33 wt% K.
  • Example 11 Preparation of No. Average Molecular Weight 360 poly(isobutylene) succinic anhydride (PIBSA 360 ) .
  • a number average molecular weight 260 poly(isobutylene) (PIB 260 , BP-Napvis XlO , 586.2 g, 2.257 moles) was charged to a one litre oil-jacketed reaction vessel.
  • the vessel was further charged with maleic anhydride (442.71 g, 4.52 moles).
  • the mixture was heated to 200°C and stirred during 24 hours. At the end of this period, the maleic anhydride was removed by vacuum distillation.
  • Example 12 Preparation of sodium salt of No. Average Molecular Weight 360 Poly(isobutylene) Succinic Acid - Na(PIBSA 3S0 ) .
  • a reactor was charged with a sample of poly(isobutylene)succinic anhydride prepared as above (412.91 g, 392.26 g PIBSA 360 , 1.096 moles, 20.65 g PIB 260 ) .
  • the vessel was further charged with Solveso 150 (526.19 g) and the liquids heated and stirred to form a homogenous deep brown solution.
  • Sodium hydroxide as dry pellets 43.84 g, 1.096 mol
  • the resulting suspension was stirred overnight at 70°C.
  • FTIR indicated complete consumption of the PIBSA and formation of carboxylic acid and carboxylic acid salt.
  • the stirring was switched off and a small amount of NaOH ( ⁇ 0.5 g) allowed to settle out whilst the solution was kept warm. The solution was carefully decanted and analysed as containing 2.35 wt% Na by AAS versus 2.56% calculated.
  • Example 13 Preparation of Sodium salt of 2-ethyl, 2- phenyl butyric acid, 1,3-Dimethyl-3, 4, 5, 6-tetrahydro- 2 (IH) -pyrimidinone (DMPU) Adduct.
  • PhEt 2 CC0 2 H (3.45 g, 20 mmol) was added to a slurry of NaH (0.48 g, 20 mmol) and DMPU (2.42 cm 3 , 10 mmol) in dry toluene (30 cm 3 ) in a dry Schlenk tube under nitrogen atmosphere.
  • the solids dissolved in a few minutes accompanied by a mild exotherm and some gas evolution to give a clear pale straw coloured solution.
  • the solution was filtered and toluene removed under vacuum until solids began to crystallise out. The solids were warmed to dissolve, then recrystallised on slow cooling, first to ambient, then -20°C.
  • Example 14 Preparation of Sodium Salt of 2-Ethyl- Hexanoic Acid, DMP ⁇ Adduct.
  • Additised fuel was prepared by dissolving the required amounts of additive or additives (depending on the test) in one litre of base diesel fuel, then diluting in the base fuel until the fuel finally contained an additional total 17 ppm m/m of total metal or metals, as appropriate, above background level.
  • Base fuel used was BPD28, as specified below.
  • Additives used were sodium and potassium salts of PIBSAs prepared from BP Napvis X-
  • test vehicle was a Peugeot 309 diesel, specified as bbeellooww,, aanndd ffiitttteedd with a 'cracked wall' trap prepared
  • the car was driven on a single rolls endurance dynamometer at steady speed and level road drag power for the unladen vehicle such that at the inlet to the trap the exhaust gas temperature was about 195°C for a clean trap.
  • the dynamometer used was outdoors and so the exact speed was a function of ambient temperature and weather conditions, typically the speed was 60 km/hr. Test duration was about 24 hrs.
  • the pressure-drop across the filter was measured using a pressure transducer and the data logged at programmed intervals.
  • a plot of pressure drop versus time yielded a characteristic 'saw-tooth' curve consisting of a series of gradual increases in pressure drop interspersed at intervals with sharp decreases associated with ignition of the trapped material and hence regeneration of the filter.
  • a typical such trace is shown as Figure 1 hereto.
  • the readings for pressure drop were taken and, using conventional techniques, the mean value of the pressure drop and the standard deviation of the pressure drop readings were determined.
  • the following table shows total ppm m/m metal above background value for each of sodium and potassium as well as the mean back pressure and the sum of mean back pressure plus twice standard deviation therein resulting from use of the listed doses in the test described above.
  • the base fuel use was BPD 29, specified as below:
  • test vehicle, trap, dynamometer, driving and monitoring methods were as detailed for the previous example.
  • the readings for pressure drop were logged.
  • the data log was taken and values at periods of engine downtime or where pressure was not changing by more than 1 mBar per minute were removed.
  • the mean and standard deviations of the values for the remaining measurements were determined by standard methods.

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Abstract

Selon un procédé permettant d'améliorer la combustion d'un carburant, et/ou d'améliorer l'oxydation des produits carbonés dérivés de la combustion ou de la pyrolyse dudit carburant, on ajoute à ce dernier, avant sa combustion, une composition contenant un mélange de deux complexes organo-métalliques ou plus de métaux du groupe I, et des additifs pour carburants contenant un mélange de deux complexes organo-métalliques ou plus de métaux du groupe I, ainsi qu'un liquide support soluble dans le carburant et miscible avec ce dernier dans toutes les proportions.
EP97918251A 1996-04-24 1997-04-24 Additifs pour carburants Withdrawn EP0904337A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
PCT/GB1996/000990 WO1996034074A1 (fr) 1995-04-24 1996-04-24 Amelioration de la combustion
WOPCT/GB96/00990 1996-04-24
GBGB9622026.4A GB9622026D0 (en) 1996-10-24 1996-10-24 Fuel additives
GB9622026 1996-10-24
PCT/GB1997/001156 WO1997040122A1 (fr) 1996-04-24 1997-04-24 Additifs pour carburants

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GB9907058D0 (en) * 1999-03-26 1999-05-19 Infineum Uk Ltd Fuel oil compositions
US8211190B2 (en) 1999-03-26 2012-07-03 Infineum International Limited Fuel oil compositions
AU2001227890A1 (en) * 2000-01-14 2001-07-24 Bio-Friendly Corporation Method for liquid catalyst delivery for combustion processes
US8177865B2 (en) 2009-03-18 2012-05-15 Shell Oil Company High power diesel fuel compositions comprising metal carboxylate and method for increasing maximum power output of diesel engines using metal carboxylate

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926580A (en) * 1974-06-27 1975-12-16 Ethyl Corp Fuel compositions and additive mixtures for alleviation of exhaust gas catalyst plugging
CA1218349A (fr) * 1983-10-17 1987-02-24 Gwan Kim Catalyseur a grande aire geometrique surfacique
GB8515974D0 (en) * 1985-06-24 1985-07-24 Shell Int Research Gasoline composition
GB8516420D0 (en) * 1985-06-28 1985-07-31 Ontario Research Foundation Diesel particulate traps
US4690687A (en) * 1985-08-16 1987-09-01 The Lubrizol Corporation Fuel products comprising a lead scavenger
GB2248068A (en) * 1990-09-21 1992-03-25 Exxon Chemical Patents Inc Oil compositions and novel additives
DE4041127A1 (de) * 1990-12-21 1992-02-20 Daimler Benz Ag Verfahren zur verringerung der schadstoffemission der verbrennungsabgase von dieselmotoren
GB2254610B (en) * 1991-04-02 1994-10-05 Ass Octel Method for the preparation of aquo and other small protic lewis base complexes of metal salts of organic acids
US5344467A (en) * 1991-05-13 1994-09-06 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
CA2149035C (fr) * 1992-11-10 2005-01-18 Jeremy D. Peter-Hoblyn Methode servant a reduire les emissions nocives d'un moteour diesel muni d'un piege a particules
AU7359194A (en) * 1993-07-12 1995-02-13 Platinum Plus, Inc. Method for reducing emissions of nox and particulates from a diesel engine
GB9315974D0 (en) * 1993-08-02 1993-09-15 Ass Octel Fuel additives
GB9508248D0 (en) * 1995-04-24 1995-06-14 Ass Octel Process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9740122A1 *

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