WO2008069981A2 - Procédé de préparation d'éthers de dibutyle à partir d'éthanol déshydraté - Google Patents

Procédé de préparation d'éthers de dibutyle à partir d'éthanol déshydraté Download PDF

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Publication number
WO2008069981A2
WO2008069981A2 PCT/US2007/024665 US2007024665W WO2008069981A2 WO 2008069981 A2 WO2008069981 A2 WO 2008069981A2 US 2007024665 W US2007024665 W US 2007024665W WO 2008069981 A2 WO2008069981 A2 WO 2008069981A2
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Prior art keywords
butanol
catalyst
ethanol
reaction product
acid
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PCT/US2007/024665
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English (en)
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WO2008069981A3 (fr
Inventor
Leo Ernest Manzer
Michael B. D'amore
Edward S. Miller
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E. I. Du Pont De Nemours And Company
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Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to EP07867595A priority Critical patent/EP2089346A2/fr
Priority to BRPI0717684-8A2A priority patent/BRPI0717684A2/pt
Priority to CA002668877A priority patent/CA2668877A1/fr
Priority to JP2009539345A priority patent/JP2010511618A/ja
Publication of WO2008069981A2 publication Critical patent/WO2008069981A2/fr
Publication of WO2008069981A3 publication Critical patent/WO2008069981A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups

Definitions

  • the present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth.
  • Dibutyl ethers are useful as diesel fuel cetane enhancers (R. Kotrba, "Ahead of the Curve", in Ethanol Producer Magazine, November 2005); an example of a diesel fuel formulation comprising dibutyl ether is disclosed in WO 2001018154.
  • the production of dibutyl ethers from butanol is known (see Karas, L. and Piel, W. J. Ethers, in Kirk-Othmer Encyclopedia of Chemical Technology, Fifth Ed., Vol. 10, Section 5.3, p.
  • ethanol can be recovered from a number of sources, including synthetic and fermentation feedstocks. Synthetically, ethanol can be obtained by direct catalytic hydration of ethylene, indirect hydration of ethylene, conversion of synthesis gas, homologation of methanol, carbonylation of methanol and methyl acetate, and synthesis by both homogeneous and heterogeneous catalysis. Fermentation feedstocks can be fermentable carbohydrates (e.g., sugar cane, sugar beets, and fruit crops) and starch materials (e.g., grains including corn, cassava, and sorghum).
  • fermentable carbohydrates e.g., sugar cane, sugar beets, and fruit crops
  • starch materials e.g., grains including corn, cassava, and sorghum
  • yeasts from the species including Saccharomyces can be employed, as can bacteria from the species Zymomonas, particularly Zymomonas mobilis.
  • Ethanol is generally recovered as an azeotrope with water, so that it is present at about 95 weight percent with respect to the weight of water and ethanol combined. See Kosaric, et. al, Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Volume 12, pages 398- 473, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, and P. L. Rogers, et al., Adv. Biochem. Eng. 23 (1982) 27-84.
  • the ethanol can be further dried by methods known in the art (see Kosaric, supra), including passing the ethanol-water azeotropic mixture over molecular sieves and azeotropic distillation of the ethanol-water mixture with an entraining agent, usually benzene.
  • Methods for producing 1-butanol from ethanol are known. It is known that 1-butanol can be prepared by condensation from ethanol over basic catalysts at high temperature using the so-called "Guerbet Reaction.” See for example, J. Logsdon in Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley and Sons, Inc., New York, 2001.
  • Some references further describing the production of 1-butanol from ethanol include: Chinese Pat. No. CN 12168383C; C.
  • the present invention relates to a process for making butyl ethers comprising: a) contacting dry ethanol with a base catalyst to make a first reaction product comprising 1-butanol; b) recovering from the first reaction product a partially-purified first reaction product consisting essentially of 1-butanol and no more than 5 weight percent water based on the weight of the 1-butanol and water combined; and c) contacting the partially-purified first reaction product of step (b), optionally in the presence of a solvent, with at least one acid catalyst at a temperature of about 50 degrees C to about 450 degrees C and a pressure from about 0.1 MPa to about 20.7 MPa to produce a second reaction product comprising at least one butyl ether, and recovering said at least one butyl ether from said second reaction product to obtain at least one recovered butyl ether.
  • the dry ethanol of step a) above can optionally be obtained from an ethanol-containing fermentation broth.
  • the dibutyl ethers produced by the processes described in this invention find use as additives for fuels, including transportation fuels such as gasoline, diesel and jet fuels.
  • the present invention relates to a process for making dibutyl ethers from dry ethanol via dry butanol.
  • dry butanol refers to a product consisting essentially of 1-butanol and no more than 5 weight percent water based on the weight of the 1-butanol and water combined.
  • the expression “consisting essentially of means herein that the 1-butanol may include small amounts of other components as long as they do not affect substantially the performance of combined 1-butanol and water in subsequent process steps.
  • the dry ethanol can be obtained from any convenient source, including fermentation using microbiological processes known to those skilled in the art.
  • the fermentative microorganism and the source of the substrate are not critical for the purposes of this invention.
  • the result of the fermentation is a fermentation broth, which is then refined to produce a stream of aqueous ethanol.
  • the refining process may comprise at least one distillation column to produce a first overhead stream that comprises ethanol and water. Once the ethanol-water azeotrope has been distilled off, one or more drying procedures can be performed so that "dry ethanol" is formed. While many drying methods are known, generally the reaction product (in this case, ethanol) is passed over a dessicant, such as molecular sieves, until the desired amount of water has been removed.
  • a dessicant such as molecular sieves
  • the dry ethanol (which may be diluted with an inert gas such as nitrogen and carbon dioxide) is contacted with at least one base (or basic) catalyst in the vapor or liquid phase at a temperature of about 150 degrees C to about 500 degrees C and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising water and butanol.
  • the first reaction product will also comprise unreacted ethanol, a variety of organic products, and water.
  • the organic products include butanols, predominantly 1 -butanol.
  • the at least one base catalyst can be a homogeneous or heterogeneous catalyst.
  • Homogeneous catalysis is catalysis in which all reactants and the catalyst are molecularly dispersed in one phase.
  • Homogeneous base catalysts include, but are not limited to, alkali metal hydroxides.
  • Heterogeneous catalysis refers to catalysis in which the catalyst constitutes a separate phase from the reactants and products. See, for example, Hattori, H. (Chem. Rev. (1995) 95:537-550) and Solid Acid and
  • a suitable base catalyst useful in the current process is either a substance which has the ability to accept protons as defined by Br ⁇ nsted, or as a substance which has an unshared electron pair with which it can form a covalent bond with an atom, molecule or ion as defined by Lewis.
  • suitable base catalysts may include, but may not be limited to, metal oxides, hydroxides, carbonates, silicates, phosphates, aluminates and combinations thereof.
  • Preferred base catalysts may be metal oxides, carbonates, silicates, and phosphates.
  • Preferred metals of the aforementioned compounds may be selected from Group 1 , Group 2, and rare earth elements of the Periodic Table. Particularly preferred metals may be cesium, rubidium, calcium, magnesium, lithium, barium, potassium and lanthanum.
  • the base catalyst may be supported on a catalyst support, as is common in the art of catalysis.
  • Suitable catalyst supports may include, but may not be limited to, alumina, titania, silica, zirconia, zeolites, carbon, clays, double-layered hydroxides, hydrotalcites and combinations thereof. Any method known in the art to prepare the supported catalyst can be used.
  • One method for preparing supported catalysts is to dissolve a metal carboxylate salt in water.
  • a support such as silica is wet with the solution, then calcined. This process converts the supported metal carboxylate to the metal oxide, carbonate, hydroxide or combination thereof.
  • the support can be neutral, acidic or basic, as long as the surface of the catalyst/support combination is basic.
  • the base catalysts of the present invention may further comprise catalyst additives and promoters that will enhance the efficiency of the catalyst.
  • the relative percentage of the catalyst promoter may vary as desired. Promoters may be selected from the Group 8 metals of the Periodic Table, as well as copper and chromium.
  • the base catalysts of the invention can be obtained commercially, or can be prepared from suitable starting materials using methods known in the art.
  • the catalysts employed for the current invention may be used in the form of powders, granules, or other particulate forms. Selection of an optimal average particle size for the catalyst will depend upon such process parameters as reactor residence time and desired reactor flow rates. Examples of methods of using base catalysts to convert ethanol to butanol are discussed in the following references.
  • U.S. Pat. No. 5,300,695 assigned to Amoco Corp. discloses processes in which an alcohol having X carbon atoms is reacted over an L- type zeolite catalyst to produce a higher molecular weight alcohol.
  • a first alcohol having X carbon atoms is condensed with a second alcohol having Y carbon atoms to produce an alcohol having X+Y carbons.
  • ethanol is used to produce butanol using a potassium L-type zeolite. J. I.
  • the higher molecular weight alcohols are yielded from ethanol as a starting material with the aid of a calcium phosphate compound, e.g., hydroxyapatite Caio(PO 4 ) 6 (OH) 2 , tricalcium phosphate Ca 3 (PO 4 J 2 , calcium monohydrogen phosphate CaHPO 4 ⁇ (0-2)H 2 O, calcium diphosphate Ca 2 P 2 O 7 , octacalcium phosphate Ca 8 H 2 (PO 4 ) 6 ⁇ 5H 2 O, tetracalcium phosphate Ca 4 (PO 4 J 2 O, or amorphous calcium phosphate Ca 3 (PO 4 ) 2 ⁇ nH 2 ⁇ , preferably hydroxyapatite, as a catalyst, the contact time being 0.4 second or longer.
  • a calcium phosphate compound e.g., hydroxyapatite Caio(PO 4 ) 6 (OH) 2 , tricalcium phosphate Ca 3 (PO 4 J 2 , calcium mono
  • the catalytic conversion of the dry ethanol to the first reaction product comprising 1-butanol and water can be run in either batch or continuous mode as described, for example, in H. Scott Fogler, (Elements of Chemical Reaction Engineering, 2 nd Edition, (1992) Prentice-Hall Inc, CA).
  • Suitable reactors include fixed-bed, adiabatic, fluid-bed, transport bed, and moving bed.
  • the catalyst may become fouled, and therefore it may be necessary to regenerate the catalyst.
  • Preferred methods of catalyst regeneration include, contacting the catalyst with a gas such as, but not limited to, air, steam, hydrogen, nitrogen or combinations thereof, at an elevated temperature.
  • the first reaction product is then subjected to a suitable refining process to produce a partially-purified first reaction product consisting essentially of 1-butanol and no more than 5 weight percent water, based on the weight of the 1-butanol and water combined.
  • a suitable refining process may include azeotropic distillation of the product to give a condensate consisting of an upper butanol rich phase of butanol and water and a lower water rich phase of butanol and water.
  • a dry butanol stream may then be recovered from the bottoms of a second distillation unit after subjecting the upper condensed phase from the first distillation unit to another azeotropic distillation.
  • the present invention relates to a process for making at least one dibutyl ether comprising contacting the partially-purified first reaction product consisting essentially of 1-butanol and no more than 5 weight percent water based on the weight of the 1 -butanol and water combined with at least one acid catalyst to produce a second reaction product comprising at least one dibutyl ether, and recovering said at least one dibutyl ether from said second reaction product to obtain at least one recovered dibutyl ether.
  • the "at least one dibutyl ether” comprises primarily di-n-butyl ether, however the dibutyl ether reaction product may comprise additional dibutyl ethers, wherein one or both butyl substituents of the ether are selected from the group consisting of 1 -butyl, 2-butyl, t-butyl and isobutyl.
  • the reaction to form at least one dibutyl ether is performed at a temperature of from about 50 degrees Celsius to about 450 degrees Celsius. In a more specific embodiment, the temperature is from about 100 degrees Celsius to about 250 degrees Celsius.
  • the reaction can be carried out under an inert atmosphere at a pressure of from about atmospheric pressure (about 0.1 MPa) to about 20.7 MPa. In a more specific embodiment, the pressure is from about 0.1 MPa to about 3.45 MPa.
  • Suitable inert gases include nitrogen, argon and helium.
  • the at least one acid catalyst can be a homogeneous or heterogeneous catalyst.
  • Homogeneous catalysis is catalysis in which all reactants and the catalyst are molecularly dispersed in one phase.
  • Homogeneous acid catalysts include, but are not limited to inorganic acids, organic sulfonic acids, heteropolyacids, fluoroalkyl sulfonic acids, metal sulfonates, metal trifluoroacetates, compounds thereof and combinations thereof.
  • Examples of homogeneous acid catalysts include sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrogen fluoride, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid.
  • Heterogeneous catalysis refers to catalysis in which the catalyst constitutes a separate phase from the reactants and products.
  • Heterogeneous acid catalysts include, but are not limited to 1 ) heterogeneous heteropolyacids (HPAs), 2) natural clay minerals, such as those containing alumina or silica, 3) cation exchange resins, 4) metal oxides, 5) mixed metal oxides, 6) metal salts such as metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, and 7) zeolites, 8) combinations of groups 1 - 7.
  • HPAs heterogeneous heteropolyacids
  • natural clay minerals such as those containing alumina or silica
  • 3) cation exchange resins such as those containing alumina or silica
  • metal oxides such as those containing
  • the heterogeneous acid catalyst may also be supported on a catalyst support.
  • a support is a material on which the acid catalyst is dispersed.
  • Catalyst supports are well known in the art and are described, for example, in Satterfield, C. N. (Heterogeneous Catalysis in Industrial Practice, 2 nd Edition, Chapter 4 (1991 ) McGraw-Hill, New York).
  • the catalyst can be separated from the reaction product by any suitable technique known to those skilled in the art, such as decantation, filtration, extraction or membrane separation (see Perry, R.H. and Green, D.W. (eds), Perry's Chemical Engineer's Handbook, 7 th Edition, Section 13, 1997, McGraw-Hill, New York, Sections 18 and 22).
  • the at least one dibutyl ether can be recovered from the reaction product by distillation as described in Seader, J. D., et al (Distillation, in Perry, R.H. and Green, D.W. (eds), Perry's Chemical Engineer's Handbook, 7 th Edition, Section 13, 1997, McGraw-Hill, New York).
  • the at least one dibutyl ether can be recovered by phase separation, or extraction with a suitable solvent, such as trimethylpentane or octane, as is well known in the art.
  • Unreacted 1-butanol can be recovered following separation of the at least one dibutyl ether and used in subsequent reactions.
  • the at least one recovered dibutyl ether can be added to a transportation fuel as a fuel additive.
  • C is degrees Celsius
  • mg is milligram
  • ml is milliliter
  • temp is temperature
  • MPa is mega Pascal
  • GC/MS gas chromatography/mass spectrometry.
  • Amberlyst® manufactured by Rohm and Haas, Philadelphia, PA
  • tungstic acid, 1-butanol and H 2 SO 4 were obtained from Alfa Aesar (Ward Hill, MA)
  • CBV-3020E was obtained from PQ Corporation (Berwyn, PA)
  • Sulfated Zirconia was obtained from Engelhard Corporation (Iselin, NJ)
  • 13% Nafion®/SiO 2 can be obtained from Engelhard
  • H-Mordenite can be obtained from Zeolyst Intl. (Valley Forge, PA).
  • Examples 1 to 13 show that the indicated catalysts were capable under the indicated conditions of producing the product dibutyl ethers. Some of the catalysts shown in Examples 1 to 13 were ineffective when utilized at suboptimal conditions (data not shown).

Abstract

La présente invention concerne un procédé de préparation d'éthers de dibutyle au moyen d'éthanol déshydraté provenant éventuellement d'un bouillon de fermentation. Les éthers de dibutyle préparés au moyen de ce procédé peuvent être utilisés en tant qu'additifs pour des carburants y compris des carburants de transport comme de l'essence et des carburants diesel.
PCT/US2007/024665 2006-12-01 2007-11-30 Procédé de préparation d'éthers de dibutyle à partir d'éthanol déshydraté WO2008069981A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP07867595A EP2089346A2 (fr) 2006-12-01 2007-11-30 Procédé de préparation d'éthers de dibutyle à partir d'éthanol déshydraté
BRPI0717684-8A2A BRPI0717684A2 (pt) 2006-12-01 2007-11-30 "processo de produção de éter butilíco"
CA002668877A CA2668877A1 (fr) 2006-12-01 2007-11-30 Procede de preparation d'ethers de dibutyle a partir d'ethanol deshydrate
JP2009539345A JP2010511618A (ja) 2006-12-01 2007-11-30 ジブチルエーテル類を乾燥エタノールから生成する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US87227606P 2006-12-01 2006-12-01
US60/872,276 2006-12-01

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WO2008069981A2 true WO2008069981A2 (fr) 2008-06-12
WO2008069981A3 WO2008069981A3 (fr) 2008-12-11

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EP (1) EP2089346A2 (fr)
JP (1) JP2010511618A (fr)
CN (1) CN101541719A (fr)
BR (1) BRPI0717684A2 (fr)
CA (1) CA2668877A1 (fr)
WO (1) WO2008069981A2 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6323383B1 (en) * 1998-01-30 2001-11-27 Kabushiki Kaisha Sangi Synthesis method of chemical industrial raw material and high-octane fuel, and high-octane fuel composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6323383B1 (en) * 1998-01-30 2001-11-27 Kabushiki Kaisha Sangi Synthesis method of chemical industrial raw material and high-octane fuel, and high-octane fuel composition

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Publication number Publication date
WO2008069981A3 (fr) 2008-12-11
JP2010511618A (ja) 2010-04-15
CN101541719A (zh) 2009-09-23
CA2668877A1 (fr) 2008-06-12
BRPI0717684A2 (pt) 2013-10-29
EP2089346A2 (fr) 2009-08-19

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