EP0529942B1 - Un procédé pour réduire la pollution atmosphérique - Google Patents

Un procédé pour réduire la pollution atmosphérique Download PDF

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Publication number
EP0529942B1
EP0529942B1 EP19920307609 EP92307609A EP0529942B1 EP 0529942 B1 EP0529942 B1 EP 0529942B1 EP 19920307609 EP19920307609 EP 19920307609 EP 92307609 A EP92307609 A EP 92307609A EP 0529942 B1 EP0529942 B1 EP 0529942B1
Authority
EP
European Patent Office
Prior art keywords
gasoline
formulated
process according
base stock
manganese tricarbonyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19920307609
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German (de)
English (en)
Other versions
EP0529942A1 (fr
Inventor
Thomas Albert Leeper
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.)
Ethyl Corp
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Ethyl Corp
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Filing date
Publication date
Application filed by Ethyl Corp filed Critical Ethyl Corp
Publication of EP0529942A1 publication Critical patent/EP0529942A1/fr
Application granted granted Critical
Publication of EP0529942B1 publication Critical patent/EP0529942B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • 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)
    • 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

Definitions

  • This invention relates to a process for reducing atmospheric pollution when gasoline is formulated to a target octane number.
  • EP-A-466511 discloses gasoline fuels which are said to be environmentally friendly and processes for the production, distribution and dispensation of such fuels.
  • the fuels have a Reid vapor pressure of 58.6 kPa according to ASTM D-323 and contain up to 1/32 gram of manganese per gallon as a cyclopentadienyl manganese tricarbonyl compound.
  • EP-A-466512 discloses a method of providing and using gasolines of suitable octane values while at the same time reducing atmospheric pollution caused by exhaust products when the gasoline is ignited.
  • the method involves blending a base fuel with a cyclopentadienyl manganese tricarbonyl compound.
  • W087/01384 discloses fuel compositions comprising as an antiknock compound a cyclopentadienyl manganese tricarbonyl compound in combination with a solvent selected from C 1-6 aliphatic alcohols and a non-leaded gasoline base.
  • the fuel compositions are said to provide improvements with respect to hydrocarbon emissions.
  • gasoline properties octane quality, volatility, stability, distillation characteristics
  • these key gasoline properties must be provided within the capabilities and production capacities of the petroleum refining industry.
  • this invention provides a process for increasing refinery capacity and decreasing refinery emissions by providing an efficacious means for formulating gasoline with a target octane number.
  • This invention is deemed to provide a most effective and efficient way of providing gasolines of suitable octane values while concomitantly reducing the potential for ground ozone formation, smog formation, and other grievous consequences of atmospheric pollution.
  • a process for reducing atmospheric pollution when gasoline is formulated to a target octane number which process comprises:
  • the gasoline-type hydrocarbon fuels used in forming the gasoline will generally comprise saturates, olefins and aromatics.
  • Oxygenated fuel blending components such as hydrocarbyl ethers, are also suitable for use.
  • the fuels contain limitations on the content of aromatic gasoline hydrocarbons, inasmuch as aromatics are capable of providing exhaust product species of relatively high reactivity.
  • a benefit associated with this invention is the ability of a refiner to decrease the severity of reformer operations in the production of gasoline.
  • the reduction in reformer severity is due in part to the obtainment of the target octane numbers by using an amount of at least one cyclopentadienyl manganese tricarbonyl compound in lieu of an amount of one or more aromatic gasoline hydrocarbons required to achieve the same target octane number.
  • a refiner is able to decrease the amount of fuel oil required for reformer operation - which in turn results in a decrease in the amount of emissions of NO x , CO, particulates, SO x , and CO 2 from the reformer furnace stack.
  • a refinery having a rated crude capacity of about 50,000 barrels per stream day (MBPSD), wherein about 50% of the rated capacity is utilized in the production of gasoline will use at least one cyclopentadienyl manganese tricarbonyl compound in an amount equivalent up to about 33 kg, for example from 10 to 33 kg, of manganese per stream day, preferably from 15 to 33 kg of manganese per stream day, and most preferably from 25 to 33 kg of manganese per 25,000 barrels of formulated gasoline per stream day.
  • the gasolines produced using the process of the invention are lead-free in the sense that no organolead antiknock agent is blended into the fuel. If any trace amounts of lead are present, such amounts are due exclusively to contamination in the system in which the fuels are formed, blended, stored, transported or dispensed.
  • the hydrocarbonaceous gasoline base stocks that can be used in forming the gasoline blends include straight run stocks, light naphtha fractions, cracked gasoline stocks obtained from thermal or catalytic cracking, hydrocracking, or similar methods, reformate obtained by catalytic reformation or like processes, polymer gasolines formed via polymerization of olefins, alkylates obtained by addition of olefins to isobutane or other hydrocarbons by alkylation processes, isomerates formed by isomerization of lower straight chain paraffins such as a n-hexane, n-heptane, and the like, and other hydrocarbons of the gasoline boiling range formed by suitable refinery processing operations.
  • Suitable amounts of appropriate hydrocarbons formed by other methods such as production from coal, shale or tar sands can be included, if desired.
  • reformates based on liquid fuels formed by the Fischer-Tropsch process can be included in the blends.
  • the resultant gasoline must satisfy the reduced total toxic compounds and the maximum reactivity tailpipe hydrocarbon emission requirements of this invention and additionally will possess the distillation characteristics typical of conventional regular, midgrade, premium, or super-premium unleaded gasolines.
  • the motor gasolines are generally within the parameters of ASTM D 4814 and typically have initial boiling points in the range of about 20 to about 46°C and final boiling points in the range of about 185 to about 225°C as measured by the standard ASTM distillation procedure (ASTM D 86).
  • the hydrocarbon composition of gasolines according to volume percentages of saturates, olefins, and aromatics is typically determined by ASTM test procedure D 1319.
  • the base gasoline will be a blend of stocks obtained from several refinery processes.
  • the final blend may also contain hydrocarbons made by other procedures such as alkylates made by the reaction of C 4 olefins and butanes using an acid catalyst such as sulfuric acid or hydrofluoric acid, and aromatics made from a reformer.
  • the saturated gasoline components comprise paraffins and naphthenates. These saturates are generally obtained from: (1) virgin crude oil by distillation (straight run gasoline), (2) alkylation processes (alkylates), and (3) isomerization procedures (conversion of normal paraffins to branched chain paraffins of greater octane quality). Saturated gasoline components also occur in so-called natural gasolines. In addition to the foregoing, thermally cracked stocks, catalytically cracked stocks and catalytic reformates contain some quantities of saturated components. In accordance with preferred embodiments of this invention, the base gasoline blend contains a major proportion of saturated gasoline components. Generally speaking, the higher the content of saturates consistent with producing a fuel of requisite octane quality and distillation characteristics, the better.
  • Olefinic gasoline components are usually formed by use of such procedures as thermal cracking, and catalytic cracking. Dehydrogenation of paraffins to olefins can supplement the gaseous olefins occurring in the refinery to produce feed material for either polymerization or alkylation processes.
  • the olefins if used in the fuel blends, should be substantially straight chain 1-olefins such as 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Olefins of this type are known to exhibit excellent antiknock response to cyclopentadienyl manganese tricarbonyls -- see Brown and Lovell, Industrial and Engineering Chemistry, Volume 50, No. 10, October 1958, pages 1547-50.
  • the gasoline base stock blends with which the cyclopentadienyl manganese tricarbonyl additive is blended pursuant to this invention will generally contain 40 to 90 volume % of saturates, up to 30 (and preferably less than 10 and more preferably less than 5) volume % olefins, and up to about 45 volume % aromatics.
  • Preferred gasoline base stock blends for use in the practice of this invention are those containing no more than 40% by volume of aromatics, more preferably no more than 30% by volume of aromatics, still more preferably no more than 28% by volume of aromatics, and most preferably no more than 25% by volume of aromatics.
  • the overall fuel blend will contain no more than 1% by volume and most preferably no more than 0.8% by volume of benzene.
  • Particularly preferred unleaded gasolines produced in the practice of this invention not only meet the emission reactivity criteria of this invention, but in addition, are characterized by having (1) a maximum sulfur content of 300 ppm, (2) a maximum bromine number of 20, (3) a maximum aromatic content of 20% by volume, (4) a maximum content of benzene of 1% by volume, and (5) a minimum content of contained oxygen of 2% by weight in the form of at least one monoether or polyether, such gasoline having dissolved therein up to about 0.03 gram of manganese per gallon as methylcyclopentadienyl manganese tricarbonyl.
  • Gasolines of this type not containing the manganese additive are sometimes referred to as reformulated gasolines. See for example Oil & Gas Journal, April 9, 1990, pages 43-48.
  • the preferred gasoline base stock blends are those having an octane rating of (R + M)/2 ranging from 78-95.
  • cyclopentadienyl manganese tricarbonyl compounds Any of a variety of cyclopentadienyl manganese tricarbonyl compounds can be used in the practice of this invention. Reference may be had, for example, to U.S.P. 2,818,417 for a description of suitable cyclopentadienyl manganese tricarbonyl compounds and their preparation.
  • the preferred compounds or mixtures of compounds are those which are in the liquid state of aggregation at ordinary ambient temperatures, such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl.
  • the most preferred compound because of its commercial availability and its excellent combination of properties and effectiveness is methylcyclopentadienyl manganese tricarbonyl.
  • the invention provides a process for increasing refinery capacity which comprises :

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (12)

  1. Procédé pour réduire la pollution atmosphérique lorsqu'une essence est formulée à un indice d'octane prédéterminé, procédé qui comprend :
    a) la réduction des émissions de NOx, CO, particules, SOx et CO2 du four d'une raffinerie équipée d'un reformeur et ayant une capacité nominale en brut de plus d'environ 7950 cm3 (environ 50 000 barrils) par jour de fonctionnement effectif, 50 % au moins de la capacité nominale étant utilisés dans la production d'essence, par conduite du reformeur à une sévérité réduite comparativement à la sévérité du reformeur requise pour atteindre l'indice d'octane prédéterminé pour une essence formulée consistant en composants de mélange du carburant de base et en une quantité d'un ou plusieurs hydrocarbures aromatiques pour l'essence, afin de produire une matière de base pour essence ;
    et
    b) à formuler l'essence à un indice d'octane prédéterminé par mélange de la matière de départ pour essence produite en a) avec au moins un composé de cyclopentadiényl-manganèse tricarbonyle en une quantité qui équivaut jusqu'à environ 33 kg de manganèse par 3975 m3 (25 000 barrils) d'essence formulée par jour de fonctionnement effectif.
  2. Procédé suivant la revendication 1, dans lequel la matière de base pour essence contient 40 à 90 % en volume d'hydrocarbures saturés, jusqu'à 30 % en volume d'oléfines et jusqu'à environ 45 % d'aromatiques.
  3. Procédé suivant la revendication 2, dans lequel la matière de base pour essence contient jusqu'à environ 30 % en volume d'aromatiques.
  4. Procédé suivant la revendication 3, dans lequel la matière de base pour essence contient jusqu'à environ 25 % en volume d'aromatiques.
  5. Procédé suivant l'une quelconque des revendications 1 à 4, dans lequel l'essence formulée ne contient pas plus de 1 % en volume de benzène.
  6. Procédé suivant la revendication 5, dans lequel l'essence formulée ne contient pas plus de 0,8 % en volume de benzène.
  7. Procédé suivant l'une quelconque des revendications 1 à 6, dans lequel la matière de base pour essence a un indice d'octane de 78 à 95.
  8. Procédé suivant l'une quelconque des revendications 1 à 7, dans lequel le composé de cyclopentadiényl-manganèse tricarbonyle est le méthylcyclopentadiénylmanganèse tricarbonyle.
  9. Procédé pour accroítre la capacité d'une raffinerie lorsque de l'essence est formulée à un indice d'octane prédéterminé, qui comprend :
    a) la réduction des émissions de NOx, de CO, de particules, de SOx et de CO2 du four d'une raffinerie équipée d'un reformeur et ayant une capacité nominale en brut de plus d'environ 7950 cm3 (environ 50 000 barrils) par jour de fonctionnement effectif, au moins 50 % de la capacité nominale étant utilisés dans la production d'essence, par conduite du reformeur à une sévérité réduite comparativement à la sévérité du reformeur nécessaire pour atteindre l'indice d'octane prédéterminé pour une essence formulée consistant en composants de mélange de base pour carburant et en une quantité d'un ou plusieurs hydrocarbures aromatiques pour essence, de manière à produire une matière de base pour essence,
    et
    b) à formuler l'essence à un indice d'octane prédéterminé par mélange de la matière de base pour essence produite en (a) avec au moins un composé de cyclopentadiényl-manganèse tricarbonyle en une quantité qui équivaut jusqu'à environ 33 kg de manganèse par 3975 m3 (25 000 barrils) d'essence formulée par jour de fonctionnement effectif.
  10. Procédé suivant la revendication 9, dans lequel la matière de base pour essence est telle que définie dans la revendication 2, 3, 4 ou 7.
  11. Procédé suivant la revendication 9 ou 10, dans lequel l'essence formulée est telle que définie dans la revendication 5 ou 6.
  12. Procédé suivant la revendication 9, 10 ou 11, dans laquelle le composé de cyclopentadiényl-manganèse tricarbonyle est le méthylcyclopentadiényl-manganèse tricarbonyle.
EP19920307609 1991-08-23 1992-08-20 Un procédé pour réduire la pollution atmosphérique Expired - Lifetime EP0529942B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74910191A 1991-08-23 1991-08-23
US749101 1991-08-23

Publications (2)

Publication Number Publication Date
EP0529942A1 EP0529942A1 (fr) 1993-03-03
EP0529942B1 true EP0529942B1 (fr) 1998-05-06

Family

ID=25012261

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920307609 Expired - Lifetime EP0529942B1 (fr) 1991-08-23 1992-08-20 Un procédé pour réduire la pollution atmosphérique

Country Status (5)

Country Link
EP (1) EP0529942B1 (fr)
JP (1) JPH05209179A (fr)
AU (1) AU663876B2 (fr)
CA (1) CA2076302C (fr)
DE (1) DE69225364D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990022557A (ko) * 1995-06-07 1999-03-25 윌리엄 씨. 오어 증기상 연소법 및 조성물 ⅱ
US9587190B2 (en) 2014-10-17 2017-03-07 Afton Chemical Corporation Fuel composition and method of formulating a fuel composition to reduce real-world driving cycle particulate emissions

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2818417A (en) * 1955-07-11 1957-12-31 Ethyl Corp Cyclomatic compounds
US2868816A (en) * 1956-11-08 1959-01-13 Ethyl Corp Process for the preparation of cyclopentadienyl manganese tricarbonyl compounds
FR2153782A6 (en) * 1971-09-21 1973-05-04 Trambouze Yves Volatile organometallic gasoline additive - causing more complete combustion by in situ formation of catalytic oxide
US4508618A (en) * 1984-06-04 1985-04-02 El Paso Products Company Increasing the octane number of natural gasoline with trifluoromethanesulfonic acid
AU6377586A (en) * 1985-08-28 1987-03-24 Orr, W.C. Nonleaded fuel composition
CA2045455C (fr) * 1990-07-13 2002-04-02 John Vincent Hanlon Carburants ameliores
CA2045706C (fr) * 1990-07-13 2002-09-17 Thomas Albert Leeper Carburants de moteur a essence aux proprietes ameliorees

Also Published As

Publication number Publication date
JPH05209179A (ja) 1993-08-20
AU2111292A (en) 1993-02-25
CA2076302C (fr) 2003-05-27
AU663876B2 (en) 1995-10-26
DE69225364D1 (de) 1998-06-10
CA2076302A1 (fr) 1993-02-24
EP0529942A1 (fr) 1993-03-03

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