EP0227176A2 - Composition oxygénée à haut indice d'octane pour combustible et méthode pour sa préparation - Google Patents

Composition oxygénée à haut indice d'octane pour combustible et méthode pour sa préparation Download PDF

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Publication number
EP0227176A2
EP0227176A2 EP86202265A EP86202265A EP0227176A2 EP 0227176 A2 EP0227176 A2 EP 0227176A2 EP 86202265 A EP86202265 A EP 86202265A EP 86202265 A EP86202265 A EP 86202265A EP 0227176 A2 EP0227176 A2 EP 0227176A2
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EP
European Patent Office
Prior art keywords
tba
methanol
isobutene
mtbe
weight
Prior art date
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Application number
EP86202265A
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German (de)
English (en)
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EP0227176A3 (fr
Inventor
Francesco Ancillotti
Ermanno Pescarollo
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SnamProgetti SpA
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SnamProgetti SpA
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Publication date
Application filed by SnamProgetti SpA filed Critical SnamProgetti SpA
Publication of EP0227176A2 publication Critical patent/EP0227176A2/fr
Publication of EP0227176A3 publication Critical patent/EP0227176A3/fr
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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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

Definitions

  • the present invention relates to an oxygenated, high-octane-number composition for fuel, and to a method for its preparation.
  • methanol has interesting high-octane-rating characteristics, such that the addition thereof to the gasolines is one of the suggested means to cope with the lead-alkyls reductions.
  • Such a use shows however a severe drawback in that methanol, when admixed with hydrocarbons, if the resulting mixtures absorb even very minor amounts of water (500-700 ppm), undergoes phase separations.
  • An indirect way of adding methanol, with no problems, to a gasoline consists in reacting it with isobutene, or with other branched C5-C7 olefins, yielding high antiknock-rating ethers which, once that they have been admixed with gasolines, do not show any longer phenomena of instability in the presence of water.
  • Such a procedure allows however small methanol amounts, practically only the stoichiometric amount, to be added, which means 57 parts by weight per each 100 parts of reacted isobutene, such parts decreasing then to 46, if on the contrary a C5 olefin, such as the isoamylenes, is used.
  • the hydration reaction shows, relatively to the etherifying reaction, a more unfavourable thermodynamics, so that, whilst it is possible to accomplish, in the etherifying step, high ( ⁇ 99%) isobutene conversions, reaching in the hydration step a conversion of 80% is practically impossible, unless extremely complex process schemes are used.
  • Another disadvantageous characteristic of the hydration is the mutual immiscibility of the reactants (H2O-olefins) with each other, which makes it necessary to use a third component, acting as a solvent.
  • the third component causes serious technical problems as for its separation and recycle, so that the production of TBA is presently carried out on a commercial scale via the reduction of tert-butyl hydro peroxide in propylene oxide syntheses.
  • a high-octane-rating composition for fuels having, as its components, methanol, TBA and MTBE, wherein the components are comprised within the following percent ranges: methanol: 30-45%, preferably 43.1% by weight; TBA : 30-45%, preferably 43.1% by weight; MTBE : 5-20%, preferably 13.8% by weight; and a method for preparing it has been surprisigly found, by which the drawbacks of the prior art are overcome.
  • the high-octane-number composition for fuel according to the invention is such that it contains, in its preferred fo rm, even 240 parts by weight of oxygen-contaning high-octane-number components per each 100 parts of reacted isobutene, as compared to the 155 parts which can be obtained by means of the complete conversion of isobutene into MTBE.
  • the high-octane-number composition in accordance with the instant invention shows considerable advantages of stability as compared to methanol alone, and also relatively to methanol-TBA mixtures, as it shall be set forth in particular in Example 2.
  • composition according to the invention is added to the gasolines in amounts comprised within the range of from 3 to 30% by weight.
  • the method according to the present invention comprises submitting a butadiene-free C4 charge, containing a percentage of isobutene of from 10 to 55%, to one or more sequential hydration treatment(s) with water, in the presence of an acidic cationic resin, in particular based on sulphonated styrene-divinylbenzene of Amberlyst 15 type, thus partly converting isobutene into TBA, separating TBA from the mixture of the other components, containing the residual isobutene, submitting the residual isobutene in said mixture to an etherifying treatment with an excess of methanol relatively to the stoichiometric amount, to the purpose of converting it into MTBE in the presence of an acidic cationic resin, in particular based on a sulphonated styrene-divinylbenzene of Amberlyst 15 type, and is characterized in that the reaction mixture (isobutene and water) is homogenised by means of
  • the methanol excess is of from 8 to 15 times as the stoichiometric amount, as referred to the residual isobutene after the hydration.
  • the method of the present invention can be carried out in particular as illustrated in the following Example 1, which is not to be understood as being limitative of the invention.
  • the reaction of TBA formation is carried out as a process of two steps in series, and the solvent is constituted by a mixture of TBA and water, which is obtained as an intermediate fraction from the TBA separation step.
  • stream 1 100 parts by weight of an olefinic chargecontaining 50% by weight of isobutene (stream 1, see herewith attached figure), added are 145.82 parts by weight of stream 6, which is a recycle stream, and is formed by 129.78 parts of TBA and 16.04 parts of water.
  • stream 6 which is a recycle stream, and is formed by 129.78 parts of TBA and 16.04 parts of water.
  • TBA is formed, from isobutene and water.
  • the reaction product (stream 2) has the following composition: Inert butenes 50 Isobutene 20.70 TBA 168.48 H2O 6.64
  • the isobutene conversion in 10 is of 58.6%.
  • the stream 4 is sent to the fractionation column 12.
  • the reaction product (stream 8) has the following composition: Inert butenes 50 Isobutene 0.08 Methanol 53.46 MTBE 16.57 TBA 0.01 H2O 0.05
  • the total isobutene conversion is thus higher than 99.8%.
  • the stream 8 is sent to the fractionation column 14, wherein a bottom fraction is obtained, which is constituted by 16.57 parts of MTBE, 51.90 parts of methanol and 0.01 parts of TBA.
  • the remaining stream constituted by C4 hydrocarbons and azeotropic methanol is recovered overhead in 14.
  • the stream 7 and stream 9 can be either used separately, or they can be combined together, 120.46 parts being obtained of a mixture of high-octane-number oxygenated compounds, which has the following composition: Methanol 43.08% TBA 43.16% MTBE 13.76%
  • a gasoline containing 25% of aromatic hydrocarbons is admixed with methanol, with methanol and TBA and with such reaction product as obtained in Example 1.
  • the ratios are so adjusted, that methanol is always 5% of the mixture.
  • mixture 3 is higher not only than that of only methanol-containing mixture, but also than the stability of the mixture con taining methanol and TBA.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP86202265A 1985-12-19 1986-12-15 Composition oxygénée à haut indice d'octane pour combustible et méthode pour sa préparation Withdrawn EP0227176A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT23290/85A IT1197464B (it) 1985-12-19 1985-12-19 Composizione per carburante ossigenata alto ottancia e metodo per la sua preparazione
IT2329085 1985-12-19

Publications (2)

Publication Number Publication Date
EP0227176A2 true EP0227176A2 (fr) 1987-07-01
EP0227176A3 EP0227176A3 (fr) 1988-03-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86202265A Withdrawn EP0227176A3 (fr) 1985-12-19 1986-12-15 Composition oxygénée à haut indice d'octane pour combustible et méthode pour sa préparation

Country Status (2)

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EP (1) EP0227176A3 (fr)
IT (1) IT1197464B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501097A1 (fr) * 1991-02-26 1992-09-02 ÖMV Aktiengesellschaft Combustible pour moteurs à combustion et application de formate de méthyl
USRE37089E1 (en) 1995-02-08 2001-03-13 Millennium Fuels Usa Llc Refining process and apparatus
USRE37142E1 (en) 1995-02-08 2001-04-24 Millennium Fuels Usa Llc Refining process and apparatus
KR100351794B1 (ko) * 2001-06-01 2002-09-05 주식회사 서현케미칼 옥탄가를 증대시키는 연료 첨가제
KR100564736B1 (ko) * 2001-06-21 2006-03-27 히로요시 후루가와 연료 조성물
US10626342B2 (en) 2015-11-23 2020-04-21 Sabic Global Technologies B.V. Process for enhancing gasoline octane boosters, gasoline boosters, and gasolines
CN115386404A (zh) * 2022-07-11 2022-11-25 中润油新能源股份有限公司 一种高清洁甲醇汽油及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB487772A (en) * 1936-11-24 1938-06-24 Conral Cleo Callis An improved liquid fuel for internal combustion engines
EP0049921A1 (fr) * 1980-10-09 1982-04-21 Stamicarbon B.V. Mélange liquide de combustible liquide pour moteurs à combustion
US4334890A (en) * 1981-02-03 1982-06-15 The Halcon Sd Group, Inc. Process for gasoline blending stocks
EP0064253A2 (fr) * 1981-04-28 1982-11-10 Veba Oel Ag Carburant léger
EP0121089A2 (fr) * 1983-03-03 1984-10-10 DEA Mineraloel Aktiengesellschaft Combustible pour moteurs
EP0171440A1 (fr) * 1983-08-20 1986-02-19 DEA Mineraloel Aktiengesellschaft Combustible pour moteurs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB487772A (en) * 1936-11-24 1938-06-24 Conral Cleo Callis An improved liquid fuel for internal combustion engines
EP0049921A1 (fr) * 1980-10-09 1982-04-21 Stamicarbon B.V. Mélange liquide de combustible liquide pour moteurs à combustion
US4334890A (en) * 1981-02-03 1982-06-15 The Halcon Sd Group, Inc. Process for gasoline blending stocks
EP0064253A2 (fr) * 1981-04-28 1982-11-10 Veba Oel Ag Carburant léger
EP0121089A2 (fr) * 1983-03-03 1984-10-10 DEA Mineraloel Aktiengesellschaft Combustible pour moteurs
EP0171440A1 (fr) * 1983-08-20 1986-02-19 DEA Mineraloel Aktiengesellschaft Combustible pour moteurs

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501097A1 (fr) * 1991-02-26 1992-09-02 ÖMV Aktiengesellschaft Combustible pour moteurs à combustion et application de formate de méthyl
US5232464A (en) * 1991-02-26 1993-08-03 Omv Aktiengesellschaft Fuel for internal combustion engines and use of methyl formate as fuel additive
AT404596B (de) * 1991-02-26 1998-12-28 Oemv Ag Treibstoff für verbrennungsmotoren und verwendung von methylformiat
USRE37089E1 (en) 1995-02-08 2001-03-13 Millennium Fuels Usa Llc Refining process and apparatus
USRE37142E1 (en) 1995-02-08 2001-04-24 Millennium Fuels Usa Llc Refining process and apparatus
KR100351794B1 (ko) * 2001-06-01 2002-09-05 주식회사 서현케미칼 옥탄가를 증대시키는 연료 첨가제
KR100564736B1 (ko) * 2001-06-21 2006-03-27 히로요시 후루가와 연료 조성물
US10626342B2 (en) 2015-11-23 2020-04-21 Sabic Global Technologies B.V. Process for enhancing gasoline octane boosters, gasoline boosters, and gasolines
CN115386404A (zh) * 2022-07-11 2022-11-25 中润油新能源股份有限公司 一种高清洁甲醇汽油及其制备方法

Also Published As

Publication number Publication date
IT8523290A0 (it) 1985-12-19
EP0227176A3 (fr) 1988-03-23
IT1197464B (it) 1988-11-30

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