EP0201955B1 - Behandlungsverfahren eines aus einem Gemisch von Kohlenwasserstoffen und Alkoholen bestehenden Brennstoffs und so hergestelltes, aus selektiver Adsorption von Wasser erhaltenes Produkt - Google Patents

Behandlungsverfahren eines aus einem Gemisch von Kohlenwasserstoffen und Alkoholen bestehenden Brennstoffs und so hergestelltes, aus selektiver Adsorption von Wasser erhaltenes Produkt Download PDF

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Publication number
EP0201955B1
EP0201955B1 EP86200666A EP86200666A EP0201955B1 EP 0201955 B1 EP0201955 B1 EP 0201955B1 EP 86200666 A EP86200666 A EP 86200666A EP 86200666 A EP86200666 A EP 86200666A EP 0201955 B1 EP0201955 B1 EP 0201955B1
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EP
European Patent Office
Prior art keywords
fuel
treatment
mixture
water
resin
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Expired
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EP86200666A
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English (en)
French (fr)
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EP0201955A1 (de
Inventor
Yves Aurelle
Christian Bernasconi
Jean Besombes-Vailhe
Edmond Julien
Henri Roques
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Elf Antar France
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Elf France SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • 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 invention relates to a method of treating a fuel composed of a mixture of hydrocarbon (s) and alcohol (s) having an alcoholic content by volume of less than 10%; it extends to a product for selective adsorption of water in the presence of polar compounds.
  • Alcohols and in particular methanol and ethanol, are alternative fuels which, added in small percentage to hydrocarbons, have the advantage of providing a fuel mixture requiring no modification or specific adjustment of traditional petrol engines.
  • these mixtures are very sensitive to the presence of traces of water which cause a phenomenon of demixing leading to separation of the liquid into two phases of different densities: an upper phase containing the majority of the hydrocarbons and a phase polar lower rich in alcohol; this demixing phenomenon is all the more marked when the temperature of the mixture is low.
  • it is impossible to rigorously avoid the presence of water in this type of mixture because of the inevitable contact of the latter with more or less humid atmospheres during storage, transport and distribution.
  • a content of 500 p.p.m. of water is sufficient to produce the demixing at 11 ° C of a mixture composed of 5% methanol and 95% of premium fuel.
  • US Pat. No. 4,279,620 describes a process for stabilizing a premium fuel / ethanol mixture, which consists in drying it by contact with a saturated solution of Ca C1 2 and with solid Ca CI 2 .
  • the implementation of such a two-step process is relatively delicate; moreover, the calcium chloride which becomes deliquescent after hydration is the source of serious difficulties in the case of a continuous industrial implementation in a fixed bed.
  • the water adsorbents commonly used in a fixed bed are essentially aluminas, molecular sieves and silica gel.
  • the regeneration of the first two adsorbents takes place at high temperatures (250 ° to 300 ° C) and leads to significant energy consumption, so that their use would make the overall energy balance of alcohol fuels unfavorable.
  • Silica gel can be regenerated at a more moderate temperature but is mechanically fragile, which makes it difficult to use.
  • the present invention proposes to provide a new process for the treatment of fuels containing alcohols in order to prevent their demixing and to stabilize their homogeneity.
  • An essential objective of the invention is to provide an economical process from an energy point of view.
  • Another objective is to ensure rapid treatment making it possible to treat large quantities of fuels with moderate quantities of adsorbents.
  • Another objective is to authorize continuous industrial implementation.
  • the invention also aims to provide a new adsorption product having a preferential affinity with respect to water, which makes it possible to carry out drying in the presence of polar compounds.
  • the treatment process targeted by the invention applies to fuels composed of a mixture of hydrocarbon (s) and alcohol (s) having an alcohol content by volume of less than 10%; this process consists in bringing the mixture into the presence of at least one ion-exchange resin, cationic, capable of dissociating strongly in ionic form in an aqueous medium, so as to adsorb part of the water dissolved in said mixture in order to to limit its water content to a value below the limit threshold for demixing of said mixture at the minimum temperature for use.
  • the ion-exchange resins mentioned above were capable of selectively fixing the water dissolved in the hydrocarbon / alcohol mixture, with good efficiency, making it easy to lower the water content of the fuel, below the demixing limit threshold (even in the case of a low value threshold corresponding to low operating temperatures expected for the fuel). These resins can be regenerated at low temperature (of the order of 120 ° C.) so that the process of the invention uses low levels of calories.
  • ion exchange resins have so far been used on an industrial scale for the exclusive purpose of demineralization or softening by ion exchange; however, certain scientific publications mention the adsorbent properties of these resins with regard to various compounds and in particular water (CE WYMORE, “Sulfonic-type cation-exchange resins as desiccants” Ind. Eng. Chem. Prod. Res. .Development 1962, Vol. 1 n ° 3, p. 173 to 178; JA BOHORQUEZ et al, "Application of strong cationic resins to the drying of organic solvents", Bull. Soc. Chim. De France, 1982, n ° 5 -6 Part I, p. 193 to 196 and p. 197 to 201).
  • it is well known to scientists specializing in this type of resins that their field of effectiveness is limited to apolar organic media.
  • the prior art teaches a person skilled in the art that the targeted resins are incapable of selectively fixing water and would preferentially fix alcohol in the application concerned, taking into account the high percentage of alcohol relative to water. eliminate that the hydrocarbon / alcohol mixtures contain.
  • the inventors rejected this prejudice and demonstrated experimentally that the targeted resins had, in a mixed hydrocarbon / alcohol medium, a selective power for adsorption of water, making it possible to eliminate most of the water initially present; this unexpected result is currently difficult to explain. Tests have shown that this selective water adsorption remains effective for fuels containing an alcohol content of less than about 10%; this area of efficiency covers the legal area of composition of hydrocarbon / alcohol fuel mixtures (decree of October 9, 1983 in the Official Journal FR).
  • a cationic resin is used, packaged in the form of alkaline or alkaline-earth salts.
  • This type of resin has the advantage of not undergoing any degradation and therefore no loss of adsorption capacity, during the regeneration phases.
  • the said resins are advantageously packaged in the form of potassium or in the form of magnesium; it is possible to use both ionic forms of resins at the same time.
  • the resin packaged in potassium form has the advantage of having a very rapid adsorption kinetics and is therefore particularly well suited to continuous processing, the fuel being brought through a fixed bed of resin.
  • the resin packaged in the form of magnesium has a much slower kinetics but a very high adsorption capacity (of the order of 5 times greater than the first); Consequently, this resin is more particularly suitable for batch processing in which it remains in situ in the fuel for long periods.
  • the combination of the two resins and of the two implementations can make it possible, in certain applications, to cope, at the same time, with a rapid increase in the water content of the fuel (requiring rapid trapping), and with a slow evolution of this content (generally requiring the fixing of large quantities of water)
  • the process of the invention can in particular be applied to hydrocarbon (s) / methanol, or hydrocarbon (s) / ethanol mixtures, optionally containing a third solvent consisting of an alcohol of higher molecular weight, in particular tert-butanol; the hydrocarbon can as well consist of a super-fuel as an ordinary fuel.
  • the comparative examples provided below relate to a fuel of known formulation (usually designated by “M3B2”), containing by volume (to within approximately 1%) 95% of super-fuel, 3% of methanol and 2% of tert-butanoi.
  • the invention extends, as such, to a product for the selective adsorption of water in the presence of polar compounds, comprising at least one cationic resin, capable of dissociating strongly in ionic form in aqueous and conditioned medium (s ) so as to contain on its ionic sites, either K ⁇ counterions, or Mg ⁇ counterions, or a coupling of two K ⁇ , Mg ⁇ counterions.
  • the resin or resins of said adsorption product are in particular constituted by strong cationic sulfonic resins or weak cationic carboxylic resins.
  • Example 1 Treatment in a fixed bed
  • the dry adsorbent is introduced over a height of 10 cm.
  • the fuel M3B2 is brought to pass through this bed, from top to bottom with a flow rate of 0.42 l / h (passage speed: 0.066 cm / s); the initial water content of this fuel is in the example of 720 mg / l. Content water is measured at the end of the bed.
  • the adsorbent according to the invention is, in this example, a cationic sulfonic resin packaged in potassium form, having a structure composed of the styrene-divinylbenzene copolymer, type "X8 (bridging rate: 8% of divinylbenzene); the particle size of this resin is between 50 and 100 mesh (resin "DOWEX 50 W manufactured by the company Dow Chemical).
  • the curves A, B, C, D of FIG. 1 illustrate the results obtained respectively for these four adsorbents (on the abscissa is the amount of cumulative fuel treated, and on the ordinate, the water content of the fuel at the outlet).
  • the adsorbent targeted by the invention proves by far the most effective and makes it possible to fix considerably greater amounts of water than the others and, therefore, to treat larger volumes of fuel for the same volume. adsorbent involved.
  • the adsorbent according to the invention is, in this example, a cationic sulfonic resin packaged in magnesium form, having the same supporting structure as above.
  • the curves E and F of FIG. 2 correspond respectively to the isotherms of these two adsorbents (on the abscissa is plotted in mg / 1 the water content of the fuel at equilibrium, and on the ordinate, in mg of water per g. D dry adsorbent, the water content of the adsorbent at equilibrium).
  • the resin according to the invention has an adsorption capacity equivalent to, or even greater than, that of the molecular sieve which is considered to be remarkable.
  • the essential advantage of the resin lies, on the one hand, in its much lower price, on the other hand, in its ease of regeneration which operates from low-level calories (120 to 140 ° C), while the regeneration of the molecular sieve requires temperatures of the order of 250 ° C to 300 ° C.
  • the demixing threshold is of the order of 800 p.p.m. of water by weight.
  • the quantity of resin to be used is only about 120 kg.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (13)

1. Behandlungsverfahren eines aus einem Gemisch von Kohlenwasserstoff(en) und Alkohol(en) bestehenden Brennstoffs, dessen Volumengehalt an Alkohol geringer ist als 10 %, um die Homogenität des besagten Gemisches zu seiner Mindestgebrauchstemperatur zu stabilisieren, dadurch gekennzeichnet, daß das besagte Verfahren darin besteht, daß das Gemisch mit mindestens einem kationischen Austauschharz zusammengebracht wird, das so beschaffen ist, daß es sich in wässriger Umgebung intensiv in ionischer Form aufspaltet, wobei ein Teil des in dem besagten Gemisch aufgelösten Wassers adsorbiert wird, um seinen Wassergehalt auf einen Wert zu beschränken, der geringer ist als der Entmischungsgrenzwert des besagten Gemisches bei der Mindestgebrauchstemperatur.
2. Behandlungsverfahren im Einklang mit Anspruch 1, dadurch gekennzeichnet, daß der Brennstoff mit mindestens einem kationischen Harz zusammengebracht wird, das in der Form alkalischer oder erdalkalischer Salze konditioniert ist.
3. Behandlungsverfahren im Einklang mit Anspruch 2, dadurch gekennzeichnet, daß der Brennstoff mit einem Harz zusammengebracht wird, das in der Form von Kalium konditioniert ist.
4. Behandlungsverfahren im Einklang mit Anspruch 2, dadurch gekennzeichnet, daß der Brennstoff mit einem Harz zusammengebracht wird, das in der Form von Magnesium konditioniert ist.
5. Behandlungsverfahren im Einklang mit Anspruch 2, dadurch gekennzeichnet, daß der Brennstoff mit zwei Harzen zusammengebracht wird, von denen das eine in der Form von Kalium und das andere in der Form von Magnesium konditioniert ist.
6. Behandlungsverfahren im Einklang mit einem der Ansprüche 2, 3, 4 oder 5, dadurch gekennzeichnet, daß man von einem oder mehreren starken kationischen Sulfoharzen Gebrauch macht.
7. Behandlungsverfahren im Einklang mit einem der Ansprüche 2, 3, 4 oder 5, dadurch gekennzeichnet, daß man von einem oder mehreren schwachen kationischen Carboxylharzen Gebrauch macht.
8. Behandlungsverfahren im Einklang mit einem der Ansprüche 1, 2, 3, 4, 5, 6 oder 7, bei dem der Brennstoff durch eine feste Schicht von Harz(en) hindurchgeleitet wird.
9. Behandlungsverfahren im Einklang mit einem der Ansprüche 1 bis 8 für die Behandlung eines aus Kohlenwasserstoff(en) und Methanol bestehenden Brennstoffs.
10. Verfahren im Einklang mit einem der Ansprüche 1 bis 8 für die Behandlung eines aus einem Gemisch von Kohlenwasserstoff(en) und Äthanol bestehenden Brennstoffs.
11. Verfahren im Einklang mit einem der Ansprüche 9 oder 10 für die Behandlung eines Brennstoffs, der u. a. ein drittes Lösungsmittel in der Form eines Alkohols von höherem Molekulargewicht, insbesondere tertiäres Butanol, enthält.
12. Verfahren im Einklang mit einem der Ansprüche 1 bis 11 für die Behandlung eines Brennstoffs, der aus einem Gemisch von klopffestem Kraftstoff und Alkohol(en) besteht.
13. Verfahren im Einklang mit einem der Ansprüche 9, 11 und 12 gemeinsam für die Behandlung eines Brennstoffs, der mengenmäßig (etwa mit einer Genauigkeit von 1 %) aus 95 % klopffestem Kraftstoff, 3 % Methanol und 2 % tertiärem Butanol besteht.
EP86200666A 1985-05-10 1986-04-21 Behandlungsverfahren eines aus einem Gemisch von Kohlenwasserstoffen und Alkoholen bestehenden Brennstoffs und so hergestelltes, aus selektiver Adsorption von Wasser erhaltenes Produkt Expired EP0201955B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8507650A FR2581558B1 (fr) 1985-05-10 1985-05-10 Procede de traitement d'un carburant compose d'un melange d'hydrocarbures et d'alcools, et produit d'adsorption selective d'eau
FR8507650 1985-05-10

Publications (2)

Publication Number Publication Date
EP0201955A1 EP0201955A1 (de) 1986-11-20
EP0201955B1 true EP0201955B1 (de) 1988-08-17

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EP86200666A Expired EP0201955B1 (de) 1985-05-10 1986-04-21 Behandlungsverfahren eines aus einem Gemisch von Kohlenwasserstoffen und Alkoholen bestehenden Brennstoffs und so hergestelltes, aus selektiver Adsorption von Wasser erhaltenes Produkt

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US (1) US4889537A (de)
EP (1) EP0201955B1 (de)
JP (1) JPS61263608A (de)
CA (1) CA1270641A (de)
DE (1) DE3660551D1 (de)
FR (1) FR2581558B1 (de)

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DE19902437C5 (de) * 1999-01-22 2017-01-12 General Electric Technology Gmbh Verfahren und Vorrichtung zum schnellen Anfahren und zur schnellen Leistungssteigerung einer Gasturbinenanlage
GB0425501D0 (en) * 2004-11-19 2004-12-22 Amersham Plc Fluoridation process
JP2013541003A (ja) * 2010-09-20 2013-11-07 ビュータマックス・アドバンスド・バイオフューエルズ・エルエルシー ブタノール含有燃料のマルチメディア評価
JP2012142174A (ja) * 2010-12-28 2012-07-26 Jx Nippon Oil & Energy Corp 燃料電池用水素製造システム及び燃料電池システム、並びに、炭化水素系燃料の脱イオン方法及び水素製造方法
WO2012115081A1 (ja) * 2011-02-21 2012-08-30 東洋紡績株式会社 有機溶剤脱水装置
JP6024131B2 (ja) * 2012-03-14 2016-11-09 東洋紡株式会社 有機溶剤脱水装置

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US2861045A (en) * 1954-11-15 1958-11-18 Exxon Research Engineering Co Catalytic metal-modified resin
US2862979A (en) * 1957-01-23 1958-12-02 Exxon Research Engineering Co Production of oxo dimer alcohols
US3442924A (en) * 1965-12-14 1969-05-06 Toyo Ethyl Kk Process for the preparation of mixed alkyl lead compounds
US3988122A (en) * 1971-06-25 1976-10-26 Chevron Research Company Motor fuel composition
US4154580A (en) * 1974-03-22 1979-05-15 Mobil Oil Corporation Method for producing a stabilized gasoline-alcohol fuel
US4087471A (en) * 1977-05-20 1978-05-02 Petro-Tex Chemical Corporation Fixed bed process for the production of t-butanol
DE2944457A1 (de) * 1979-11-03 1981-05-14 EC Erdölchemie GmbH, 5000 Köln Verfahren zur herstellung eines gemisches, bestehend im wesentlichen aus iso-buten-oligomeren und methyl-tert.-butyl-ether, seine verwendung und treibstoffe, enthaltend ein solches gemisch
US4279620A (en) * 1980-04-07 1981-07-21 Texaco Inc. Novel process for treating gasahol
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US4383836A (en) * 1980-05-23 1983-05-17 Texaco Inc. Method for treating an aqueous ethanol mixture
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US4629710A (en) * 1984-12-20 1986-12-16 Smith Jr Lawrence A Resin catalysts and method of preparation

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Publication number Publication date
DE3660551D1 (en) 1988-09-22
JPS61263608A (ja) 1986-11-21
EP0201955A1 (de) 1986-11-20
US4889537A (en) 1989-12-26
FR2581558B1 (fr) 1987-06-26
CA1270641A (fr) 1990-06-26
FR2581558A1 (fr) 1986-11-14

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