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WO2010071595A1 - Liquide à base d'éthanol contenant un dénaturant - Google Patents

Liquide à base d'éthanol contenant un dénaturant Download PDF

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Publication number
WO2010071595A1
WO2010071595A1 PCT/SE2009/051480 SE2009051480W WO2010071595A1 WO 2010071595 A1 WO2010071595 A1 WO 2010071595A1 SE 2009051480 W SE2009051480 W SE 2009051480W WO 2010071595 A1 WO2010071595 A1 WO 2010071595A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethanol
double bond
chemical
cas
liquid
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.)
Ceased
Application number
PCT/SE2009/051480
Other languages
English (en)
Inventor
Roger Mattebo
Leif JÖNSSON
Björn Alriksson
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.)
Sekab Biofuels & Chemicals AB
Original Assignee
Sekab Biofuels & Chemicals AB
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 Sekab Biofuels & Chemicals AB filed Critical Sekab Biofuels & Chemicals AB
Publication of WO2010071595A1 publication Critical patent/WO2010071595A1/fr
Anticipated expiration legal-status Critical
Ceased 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 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
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones

Definitions

  • T-Rod It is used for example in alcohol stoves and for stain removal.
  • the liquid usually consists of 95 % v/v ethanol.
  • Other components are denaturants in the form of methyl ethyl ketone (MEK), acetone, ethyl acetate and Bitrex®.
  • MEK methyl ethyl ketone
  • acetone acetone
  • ethyl acetate ethyl acetate
  • Bitrex® methyl ethyl ketone
  • E85 is an established vehicle fuel. The symbol represents a mixture of about 85 % v/v ethanol with about 15 % v/v gasoline. A number of other components are present in the mixture in a low concentration, including denaturants.
  • Sweden the liquid described above is used as a vehicle fuel during the six months of summer.
  • the admixture of gasoline is increased, such that the gasoline portion may comprise 25 % v/v.
  • the proportion of denatured ethanol can be increased to more than 85 % v/v, up to 95 % v/v.
  • This fuel mixture has been denoted ED95.
  • the Medical Products Agency may allow the import or sale of technical-grade alcohol without denaturation, if there are special reasons and no risk of misuse.
  • otto engines used in Sweden as denaturants in ethanol fuels for combustion engines (otto engines) and compression engines (diesel engines) are for example iso-butanol and normal butanol, as well as methyl tert-butyl ether (MTBE) or ethyl tert-butyl ether (ETBE).
  • MTBE methyl tert-butyl ether
  • EBE ethyl tert-butyl ether
  • the chemical in the amount given, the chemical must not be so toxic/harmful, that a person, who nevertheless consumes the liquid, risks death or severe injury, but the rationale and aim of the addition of denaturant is that the denatured liquid should have such a repulsive smell and taste that no one wants to drink it, as well as causing vomiting on consumption,
  • Ri and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy and ethoxy.
  • y is a single bond
  • ⁇ and ⁇ are both single bonds or both double bonds.
  • Ri and R 2 are not both hydrogen
  • Ri is different from
  • R 2 is hydrogen while Ri is selected from the group consisting of methyl, ethyl, methoxy and ethoxy.
  • the chemical is not dimethyl-tetrahydrofuran.
  • the above embodiments may be combined in any desired fashion.
  • the chemical may be any organic compound.
  • Ri is selected from the group consisting of hydrogen, methyl, ethyl, methoxy and ethoxy or from the group consisting of methyl, ethyl, methoxy and ethoxy.
  • the chemical is selected from the group consisting of 2-methyltetrahydrofuran (CAS 96-47-9), 2-ethylfuran (CAS 3208-16-0), 2-methoxyfuran (CAS 25414-22-6), 2- ethoxytetrahydrofuran (CAS 13436-46-9) and tetrahydrofuran (CAS 109-99-
  • the chemical is 2- methyltetrahydrofuran (CAS 96-47-9).
  • CAS 96-47-9 2- methyltetrahydrofuran
  • denaturant is meant a chemical which, if present in an ethanol- based liquid in a sufficient amount, has such a repulsive smell that it discourages consumption and when consumed may cause vomiting, yet is not so toxic/harmful that a person, who nevertheless consumes such an ethanol-based liquid comprising the denaturant, risks death or serious injury. Furthermore, it is preferable that a denaturant is difficult to separate from ethanol.
  • “Explicit denaturation” refers to inherent denaturing capacity, i.e. the capacity to achieve a denaturing effect in an ethanol-based liquid without admixture of other denaturants.
  • “Other denaturants” refer to commercially available chemicals that have been used as denaturants, for example those that have been approved as denaturants according to national regulations. Examples of other denaturants are methanol, n-propanol, /so-propanol, isobutanol, sec-butanol, n-butanol, tert-butanol, and those described above in “List 2".
  • the other denaturant may also be MTBE or ETBE.
  • it is n-propanol, /so- propanol, isobutanol, sec-butanol, ⁇ -butanol or terf-butanol, more preferably isobutanol.
  • the amount of chemical to mix into the liquid is at least 0.5 % w/w, preferably at least 1 % w/w.
  • the amount may be adjusted on a case-by-case basis, i.e. for each ethanol-based liquid and each chemical.
  • the amount is at most 10 % w/w, such as at most 5 % w/w.
  • the percentages given here refer to percent of the liquid after addition according to the inventive method.
  • the manner of adding the chemical makes no difference, i.e. whether it is added in one portion of the mixture, for example the ethanol portion, or in the final mixture.
  • the present invention also encompasses a product in the form of an ethanol-based liquid in which the ethanol part is predominant, comprising denaturant(s) including a specific denaturant in an amount of less than 15 % v/v, characterized in that the specific denaturant is a chemical according to formula I, wherein ⁇ is a single or double bond, ⁇ is a single or double bond, Y is a single or double bond if both ⁇ and ⁇ are single bonds, Y is a single bond if ⁇ or ⁇ is a double bond, and Ri and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy and ethoxy.
  • Different embodiments of chemicals according to formula I are described above. These can be combined in any desired manner.
  • the specific denaturant is selected from the group consisting of 2-methyltetrahydrofuran (CAS 96-47-9), 2-ethylfuran (CAS 3208-16-0), 2-methoxyfuran (CAS 25414-22-6), 2- ethoxytetrahydrofuran (CAS 13436-46-9) and tetrahydrofuran (CAS 109-99- 9).
  • the specific denaturant is 2-methyltetrahydrofuran (CAS 96-47-9).
  • the ethanol portion being predominant means that it is larger by volume than any other component of the ethanol-based liquid.
  • the ethanol portion is for example greater than the portion of water, gasoline or any additive.
  • the liquid suitably comprises ethanol in an amount of at least 50 % v/v, and it is preferred that the ethanol portion is at least 75 % v/v, such as at least 80 % v/v. With regard to the denaturing effect, ethanol in an amount of at least 85 % v/v is optimal.
  • the concentration of the specific denaturant in the mixture i.e. in the ethanol-based liquid, is at least 0,5 % w/w, preferably at least 1 % w/w. According to alternative or supplementary embodiments, the concentration of the specific denaturant is at most 10 % w/w, such as at most 5 % w/w.
  • the different components of the liquid are characterized, in this document, both in terms of % v/v and % w/w, but, according to well-established conventions within the field, the unit % v/v (volume percent) is used for ethanol as well as for hydrocarbons, primarily gasoline, whereas the unit % w/w (weight percent) is used for chemicals that are added in small or very small amounts. These units may be converted into each other using the density of the chemical.
  • the ethanol- based liquid consists of a vehicle fuel, wherein the supplementary fuel portion is a liquid hydrocarbon-based fuel, except when the fuel consist exclusively of ethanol.
  • the supplementary fuel portion is a liquid hydrocarbon-based fuel, except when the fuel consist exclusively of ethanol.
  • the fuel consist exclusively of ethanol is meant those cases where ethanol is the only fuel component.
  • additives that have a main purpose other than to serve as fuel may be present in the ethanol-based liquid. Examples of such additives are denaturants, corrosion inhibitors and lubricants.
  • Liquid hydrocarbon-based fuel refers to a liquid fuel consisting primarily of hydrocarbons, i.e. chemical compounds solely comprising carbon and hydrogen.
  • the liquid hydrocarbon-based fuel may for example be obtainable from petroleum.
  • One example of a liquid, hydrocarbon-based fuel is gasoline, which may comprise octane boosting or other additives.
  • the invention also relates to the use of a chemical according to formula I, wherein ⁇ is a single or double bond, ⁇ is a single or double bond, y is a single or double bond if both ⁇ and ⁇ are single bonds, v is a single bond if ⁇ or ⁇ is a double bond, and Ri and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, methoxy and ethoxy, for denaturing of an ethanol-based liquid, in which liquid the ethanol portion is predominant.
  • Different embodiments of chemicals according to formula I are described above. These can be combined in any desired manner.
  • the chemical is selected from the group consisting of 2-methyltetrahydrofuran (CAS 96-47-9), 2-ethylfuran (CAS 3208-16-0), 2-methoxyfuran (CAS 25414-22-6), 2- ethoxytetrahydrofuran (CAS 13436-46-9) and tetrahydrofuran (CAS 109-99-
  • the chemical is 2- methyltetrahydrofuran (CAS 96-47-9).
  • the ethanol-based liquid according to the method, product or use above may comprise ethanol in an amount of at least 50 % v/v, for example at least 75, 80, 85 or 90 % v/v.
  • the denaturants according to the invention possess a denaturing effect of their own.
  • the agents may have an effect on other added denaturants such that they resist, to a surprisingly large extent, attempts at complete removal thereof from an ethanol-based liquid.
  • the denaturants according to the invention are prepared from renewable starting materials, for example biomass, such as lignocellulosic material. Because ethanol is usually prepared from renewable sources and dominate the liquids in question in terms of relative amounts, denaturants according to the invention that are prepared for example from lignocellulosic materials contribute to a larger environmental value in the product. Best mode
  • the vehicle fuel E85 is regularly denatured by addition of 0,5 % w/w isobutanol (4,000 mg/l) and 2,5 % w/w MTBE, i.e. methyl tert-butyl ether (20,000 mg/l).
  • This liquid was subjected to polar extraction and purification with activated carbon.
  • the purified ethanol/water mixture contained no trace of MTBE, while a small amount of the added isobutanol remained, 54 mg/l to be precise.
  • all the added MTBE and a large portion of the added isobutanol was transferred to the gasoline phase, which, as is evident from the above, may be removed from the mixture, i.e. from the ethanol-based liquid. This result is unsatisfactory in terms of denaturation.
  • the experiment was repeated, replacing the conventional denaturant MTBE by a denaturant according to the invention, namely MTHF, i.e. 2- methyltetrahydrofuran. All other conditions were as for the experiment described above.
  • the ethanol/water mixture contained 800 mg/l MTHF and 2,100 mg/l isobutanol. As is readily apparent, a large portion of the added MTHF remains in the ethanol/water mixture after the described purification treatment. MTHF has, in itself, a denaturing effect.
  • the water content given in the table refers to the water content in the mixture after addition of water to the ethanol-based liquid for purification purposes.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne un procédé de dénaturation explicite de liquides à base d'éthanol et/ou d'ajout de capacité de dénaturation à d'autres dénaturants dans des liquides à base d'éthanol, c'est-à-dire des liquides composés essentiellement d'éthanol, par ajout d'une substance chimique organique. Ledit procédé est caractérisé en ce que la substance chimique ajoutée est représentée par la formule (I), dans laquelle α est une liaison simple ou double, β est une liaison simple ou double, y est une liaison simple ou double à condition que α et β soient des liaisons simples, v est une liaison simple à condition que α ou β soit une liaison double, et R1 et R2 sont sélectionnés indépendamment dans le groupe constitué par hydrogène, méthyle, éthyle, méthoxy et éthoxy.
PCT/SE2009/051480 2008-12-19 2009-12-21 Liquide à base d'éthanol contenant un dénaturant Ceased WO2010071595A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0802623-9 2008-12-19
SE0802623 2008-12-19

Publications (1)

Publication Number Publication Date
WO2010071595A1 true WO2010071595A1 (fr) 2010-06-24

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ID=42269048

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2009/051480 Ceased WO2010071595A1 (fr) 2008-12-19 2009-12-21 Liquide à base d'éthanol contenant un dénaturant

Country Status (1)

Country Link
WO (1) WO2010071595A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062354A1 (fr) * 2002-01-21 2003-07-31 Ramar Ponniah Combustible à hydrocarbures
WO2004014304A2 (fr) * 2002-08-07 2004-02-19 Smithkline Beecham Corporation Compositions pharmaceutiques amorphes electriquement filees
CN1876775A (zh) * 2006-07-10 2006-12-13 曲阜速豹能源科技有限公司 一种新型清洁环保车用甲醇汽油
WO2008096257A1 (fr) * 2007-02-08 2008-08-14 Aurobindo Pharma Limited Procédé perfectionné pour la préparation de rosuvastatine calcique
WO2009113080A1 (fr) * 2008-03-12 2009-09-17 Ramar Ponnupillai Nouveau combustible hydrocarboné biologique à base de vélar

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062354A1 (fr) * 2002-01-21 2003-07-31 Ramar Ponniah Combustible à hydrocarbures
WO2004014304A2 (fr) * 2002-08-07 2004-02-19 Smithkline Beecham Corporation Compositions pharmaceutiques amorphes electriquement filees
CN1876775A (zh) * 2006-07-10 2006-12-13 曲阜速豹能源科技有限公司 一种新型清洁环保车用甲醇汽油
WO2008096257A1 (fr) * 2007-02-08 2008-08-14 Aurobindo Pharma Limited Procédé perfectionné pour la préparation de rosuvastatine calcique
WO2009113080A1 (fr) * 2008-03-12 2009-09-17 Ramar Ponnupillai Nouveau combustible hydrocarboné biologique à base de vélar

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