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WO1992004385A1 - Carburants et adjuvants de carburant - Google Patents

Carburants et adjuvants de carburant Download PDF

Info

Publication number
WO1992004385A1
WO1992004385A1 PCT/GB1991/001503 GB9101503W WO9204385A1 WO 1992004385 A1 WO1992004385 A1 WO 1992004385A1 GB 9101503 W GB9101503 W GB 9101503W WO 9204385 A1 WO9204385 A1 WO 9204385A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
diesel fuel
guanidine
aliphatic hydrocarbon
polyisobutene
Prior art date
Application number
PCT/GB1991/001503
Other languages
English (en)
Inventor
Philip Kenneth Gordon Hodgson
Linda Joy Rainbow
Nevin John Stewart
Original Assignee
The British Petroleum Company Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The British Petroleum Company Plc filed Critical The British Petroleum Company Plc
Publication of WO1992004385A1 publication Critical patent/WO1992004385A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to additives for diesel fuels and diesel fuels containing such additives.
  • deposits can form on various parts of the combustion chamber and piston.
  • One place where deposits can form is on piston crown lands. Deposits in such places are particularly undesirable because it is believed that they may contribute to undesirable polishing of the bore of the engine cylinder.
  • a favoured detergent additive is based on succinic acid derivatives having a long hydrocarbon chain, usually derived from polyisobutene.
  • succinic acid derivatives having a long hydrocarbon chain usually derived from polyisobutene.
  • EP 198 680 discloses a method of making such compounds, for example 1,5,7-triazabicyclo[4,4,0]dec-5-ene. This material is referred to in the specification as TBD. The only use suggested in EP 198 680 for such compounds is as catalysts for various chemical reactions.
  • a novel chemical compound suitable for use as a diesel fuel additive is a bicyclic guanidine substituted on the amino nitrogen atom by an aliphatic hydrocarbon group containing from 20 to 200 carbon atoms in the molecule.
  • a diesel fuel comprises a major amount of a hydrocarbon fraction having a boiling point in the range 160-380 ⁇ C at atmospheric pressure and a minor amount of a guanidine substituted on the amino nitrogen atom by an aliphatic hydrocarbon substituent having from 1 to 200 carbon atoms.
  • a further aspect of the present invention is the use of a guanidine substituted on the amino nitrogen atom by an aliphatic hydrocarbon having from 1 to 200 carbon atoms in a diesel fuel to reduce deposit formation in a diesel engine.
  • the preferred guanidines are bicyclic guanidines.
  • the preferred bicyclic guanidine is TBD.
  • the TBD may be prepared by any suitable process for example that disclosed in EP 198 680.
  • the aliphatic substituent preferably contains 1 to 200 carbon atoms, more preferably 10 to 100, most preferably 20 to 60.
  • the aliphatic group is a hydrocarbyl group, preferably derived from a polyisobutene. Such polyisobutenes having various molecular weights are commercially available. They will generally be materials of varying chain length. Where the substituent is derived from a material which is a mixture of homologues of varying chain length then the number of carbon atoms in the substituent for the purposes of this specification corresponds to the average number of carbon atoms.
  • the average number of carbon atoms can be obtained by dividing by the molecular weight of the carbon repeating unit, e.g. for polybutene the average number of carbon atoms is obtained by dividing the molecular weight by 14.
  • the bicyclic guanidines with an aliphatic substituent containing from 20 to 200 carbon atoms are believed to be new compounds.
  • the novel substituted bicyclic guanidines of the present invention may be prepared by reaction of a chlorinated aliphatic hydrocarbon and a bicyclic guanidine.
  • the chlorinated aliphatic hydrocarbon may contain a quantity of chlorine equivalent to 1 to 5 chlorine atoms per molecule, for example an amount of chlorine equivalent to 1.5 to 2.5 chlorine atoms per molecule.
  • the quantity of the guanidine derivative used in the diesel fuel may vary over a moderately wide range, and may be for example from 50 to 500, or more preferably 100 to 300 ppm.
  • Figures 1 and 2 are graphical representations of deposits resulting from heating distillate diesel fuel and by reference to the following experiments, in which comparative tests not according to the invention, are identified by letters and examples of the invention are identified by numbers.
  • the starting material was a polyisobutene supplied by BP Chemicals Limited under the trade name "Hyvis 150".
  • the polyisobutene has the following characteristics:
  • the average molecular weight was 2400.
  • the corresponding average number of carbon atoms was 171.4.
  • the chlorination was carried out in a flask fitted with a mechanical gas recycle stirrer, a reflux condenser, a thermometer pocket, a chlorine inlet with a sintered plug, and a vent to a chlorine scrubber.
  • the polyisobutene was added to the flask and the apparatus was flushed with nitrogen before it was heated to 110 ⁇ C. Chlorine gas was then fed into the apparatus at a rate of about 5 litres per hour measured at ambient temperature and pressure. The chlorination was carried out at atmospheric pressure. The apparatus was weighed before and after the addition of chlorine to indicate the chlorine uptake. Chlorine was fed for nine hours into 0.27 moles of the polyisobutene. A 20g increase in weight was obtained. Analysis showed the presence of 3.4% by weight of chlorine, which was equivalent to 2.4 chlorine atoms per molecule of the polyisobutene.
  • the apparatus used for this reaction was a two neck flask fitted with a reflux condenser and magnetic stirrer.
  • the polyisobutene chloride produced in the first step was dissolved in xylene and the apparatus flushed with nitrogen.
  • 1,5,7-triaza bicyclo (4,4,0) dec-5-ene (TBD) was added in an amount to give a molar/ratio of 2:1 to the chlorinated polyisobutene after the apparatus was flushed with nitrogen.
  • TBD 1,5,7-triaza bicyclo (4,4,0) dec-5-ene
  • the mixture was then heated to reflux for 6 hours.
  • the resulting product was then washed with a hot 10% aqueous solution of sodium hydroxide to remove hydrogen chloride liberated in the reaction.
  • the organic layer resulting from the washing step was separated and dried with magnesium sulphate. It was then filtered and evaporated to constant weight on a rotary evaporator to remove the xylene solvent.
  • the reaction product has a base number of 14.6 mg KOH per gram. This was equivalent to 67% reaction of the chlorine end groups. Evaluation of the Additive in a Diesel Fuel
  • the substituted TBD from the preceding step was added to a base fuel.
  • the base fuel was a typical winter grade diesel fuel for road vehicles.
  • the amount of additive used was sufficient to give a content of 100 ppm in the fuel.
  • the tendency of the fuel to give deposits on piston crown lands was investigated by passing the fuel over the surface of a standard aluminium tube as used in the JFTOT test (ASTMD 3241) maintained at 300°C. The fuel was passed over it on a single pass basis for a period of 2 hours.
  • Example 2 An experiment was carried out as in Example 1 except that the polyisobutene used was a material sold under the trade name "Hyvis
  • the average molecular weight was 1300.
  • the corresponding average number of carbon atoms was 92.9.
  • the chlorinated product contained 1.93 chlorine atoms per molecule of the polyisobutene, and 56% of the chlorinated product reacted to give TBD functionalised polyisobutene.
  • Comparative test A The deposit formation resulting from the use of the base fuel without any additive was determined. The results are shown in
  • a methyl substituted TBD was prepared using the general technique as disclosed in Example 1. The result of adding this to diesel fuel is shown in Figure 1, by the continuous line marked 5. A consideration of the results shown in Figure 1 shows that the use of the TBD derivatives results in a reduction in deposit formation. Deposit formation is still high with the methyl derivative, it is lower with the material derived from a relatively long chain polyisobutene, but is lowest with a material derived from a relatively short chain polyisobutene.
  • Example 5 An experiment was carried out as in Example 2 except that a lower accelerating voltage (6 kV instead of 9 kV) was used in the SEM/EDX measurements.
  • the carbon/aluminium ratios (which are an indicator of deposit thickness), along the length of the tube are shown in Figure 2, by the solid line marked 6.
  • Example 4 An experiment was carried out as in Example 4 except that the polyisobutene starting material was a material supplied by BP Chemicals Limited under the trade name "Hyvis 3". This had the following characteristics:
  • the average molecular weight was 650.
  • the corresponding average number of carbon atoms was 46.4.
  • the chlorinated polyisobutene contained 4 chlorine atoms per molecule, and 65% of the chlorinated material reacted to give TBD functionalised polyisobutene.
  • Comparative Test C A commercially available package for addition to diesel fuels sold under the designation ECA 12278 was tested as in Example 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

On décrit de nouvelles guanidines bicycliques substituées dans le groupe amine par un hydrocarbure aliphatique possédant de 20 à 100 atomes de carbone, ainsi que l'utilisation de ces guanidines substituées dans le groupe amine comme adjuvants de carburant Diesel pour réduire la formation de dépôts dans des moteurs Diesel.
PCT/GB1991/001503 1990-09-06 1991-09-04 Carburants et adjuvants de carburant WO1992004385A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9019440.8 1990-09-06
GB909019440A GB9019440D0 (en) 1990-09-06 1990-09-06 Fuels and fuel additives

Publications (1)

Publication Number Publication Date
WO1992004385A1 true WO1992004385A1 (fr) 1992-03-19

Family

ID=10681742

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/001503 WO1992004385A1 (fr) 1990-09-06 1991-09-04 Carburants et adjuvants de carburant

Country Status (3)

Country Link
AU (1) AU8493691A (fr)
GB (1) GB9019440D0 (fr)
WO (1) WO1992004385A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2276170A (en) * 1993-02-17 1994-09-21 British Tech Group Polymeric compounds
EP0757092A1 (fr) * 1995-07-31 1997-02-05 Tonen Corporation Composition de gazole
US5968499A (en) * 1995-02-16 1999-10-19 Btg International Limited Polymeric compounds
FR2817871A1 (fr) * 2000-12-12 2002-06-14 Elf Antar France Composes guanidinoalkyles, leur preparation et leur utilisation comme additifs pour carburants et lubrifiants

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB796996A (en) * 1956-03-29 1958-06-25 Monsanto Canada Ltd Imidazole derivatives
US3062630A (en) * 1960-03-23 1962-11-06 Exxon Research Engineering Co Antistatic additives
US3864098A (en) * 1974-01-07 1975-02-04 Chevron Res Fuel additives
US4011057A (en) * 1974-04-16 1977-03-08 E. I. Du Pont De Nemours And Company Hindered phenol antioxidant composition containing an amino compound
US4159898A (en) * 1974-09-10 1979-07-03 Institut Francais Du Petrole Alkyl-guanidino-heterocyclic compounds, their manufacture and use as additives for fuels and lubricants
EP0113582A2 (fr) * 1982-12-27 1984-07-18 Exxon Research And Engineering Company Polyamine macrocyclique et polyamine polycyclique additifs multifonctionnels pour huile lubrifiante
US4490293A (en) * 1982-08-02 1984-12-25 Petrolite Corporation 2,5,6,8,9-Penta-alkyl or penta-aralkyl-substituted 1,3,7-triazabicyclo(3,3,1) non-3-enes and trialkyl or triaralkyl-substituted tetrahydropyrimidines
EP0301638A2 (fr) * 1987-07-31 1989-02-01 ENICHEM SYNTHESIS S.p.A. Procédé de préparation de N-alkylcarbamates

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB796996A (en) * 1956-03-29 1958-06-25 Monsanto Canada Ltd Imidazole derivatives
US3062630A (en) * 1960-03-23 1962-11-06 Exxon Research Engineering Co Antistatic additives
US3864098A (en) * 1974-01-07 1975-02-04 Chevron Res Fuel additives
US4011057A (en) * 1974-04-16 1977-03-08 E. I. Du Pont De Nemours And Company Hindered phenol antioxidant composition containing an amino compound
US4159898A (en) * 1974-09-10 1979-07-03 Institut Francais Du Petrole Alkyl-guanidino-heterocyclic compounds, their manufacture and use as additives for fuels and lubricants
US4490293A (en) * 1982-08-02 1984-12-25 Petrolite Corporation 2,5,6,8,9-Penta-alkyl or penta-aralkyl-substituted 1,3,7-triazabicyclo(3,3,1) non-3-enes and trialkyl or triaralkyl-substituted tetrahydropyrimidines
EP0113582A2 (fr) * 1982-12-27 1984-07-18 Exxon Research And Engineering Company Polyamine macrocyclique et polyamine polycyclique additifs multifonctionnels pour huile lubrifiante
EP0301638A2 (fr) * 1987-07-31 1989-02-01 ENICHEM SYNTHESIS S.p.A. Procédé de préparation de N-alkylcarbamates

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2276170A (en) * 1993-02-17 1994-09-21 British Tech Group Polymeric compounds
GB2276170B (en) * 1993-02-17 1997-04-16 British Tech Group Polymers containing guanidine groups for use in therapy
US5698190A (en) * 1993-02-17 1997-12-16 British Technology Group Ltd. Polymeric compounds
US5851518A (en) * 1993-02-17 1998-12-22 British Technology Group Limited Polymeric compositions
US5880208A (en) * 1993-02-17 1999-03-09 Btg International Limited Polymer compounds
US6132706A (en) * 1993-02-17 2000-10-17 Btg International Limited Methods of medical treatment for excess phosphate using guanidino-containing polymers
US5968499A (en) * 1995-02-16 1999-10-19 Btg International Limited Polymeric compounds
EP0757092A1 (fr) * 1995-07-31 1997-02-05 Tonen Corporation Composition de gazole
US5730762A (en) * 1995-07-31 1998-03-24 Exxon Research And Engineering Company Gas oil (law451)
FR2817871A1 (fr) * 2000-12-12 2002-06-14 Elf Antar France Composes guanidinoalkyles, leur preparation et leur utilisation comme additifs pour carburants et lubrifiants
WO2002048212A1 (fr) * 2000-12-12 2002-06-20 Totalfinaelf France Composes guanidinoalkyles, leur preparation et leur utilisation comme additifs pour carburants et lubrifiants

Also Published As

Publication number Publication date
AU8493691A (en) 1992-03-30
GB9019440D0 (en) 1990-10-24

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