EP2089346A2 - Process for making dibutyl ethers from dry ethanol - Google Patents

Process for making dibutyl ethers from dry ethanol

Info

Publication number
EP2089346A2
EP2089346A2 EP07867595A EP07867595A EP2089346A2 EP 2089346 A2 EP2089346 A2 EP 2089346A2 EP 07867595 A EP07867595 A EP 07867595A EP 07867595 A EP07867595 A EP 07867595A EP 2089346 A2 EP2089346 A2 EP 2089346A2
Authority
EP
European Patent Office
Prior art keywords
butanol
catalyst
ethanol
reaction product
acid
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.)
Withdrawn
Application number
EP07867595A
Other languages
German (de)
French (fr)
Inventor
Leo Ernest Manzer
Michael B. D'amore
Edward S. Miller
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2089346A2 publication Critical patent/EP2089346A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

The present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth. The dibutyl ethers made by this process find use as additives for fuels, including transportation fuels such as gasoline and diesel fuels.

Description

TITLE Process for Making Dibutyl Ethers from Dry Ethanol
FIELD OF THE INVENTION The present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth.
BACKGROUND
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. 576) and is generally carried out via the dehydration of n-butyl alcohol by sulfuric acid, or by catalytic dehydration over ferric chloride, copper sulfate, silica, or silica- alumina at high temperatures. The dehydration of butanol to dibutyl ethers results in the formation of water, and thus these reactions have historically been carried out in the absence of water.
Efforts directed at improving air quality and increasing energy production from renewable resources have resulted in renewed interest in alternative fuels, such as ethanol and butanol, that might replace gasoline and diesel fuel, or be additives in these fuels as well as others.
It is known that 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).
When fermentation is used, 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. Yang and Z. Meng, J. of Catalysis (1993), 142(1 ), 37-44; A. S. Ndou, N. Plint, and N. J. Coville, Applied Catalysis, A: General (2003), 251 (2), 337-345; T. Takahashi, Kogyo Kagaku Zasshi (1946), 49 113-114; T. Takahashi, Kogyo Kagaku Zasshi (1946), 49 114-115; V. Nagarajan, N. R. Kuloor, Indian Journal of Technology (1966), 4(2), 46-54; V. Nagarajan, Chemical Processing & Engineering (Bombay) (1970), 4(11 ), 29-31 , 38; V. Nagarajan, Indian Journal of Technology (1971 ), 9(10), 380-386; V. Nagarajan, Chemical Processing & Engineering (Bombay) (1971 ), 5(10), 23-27; K. W. Yang, X. Z. Jiang and W. C. Zhang, Chinese Chemical Letters (2004), 15(112), 1497-1500; K. Yang, W. Zhang, and X. Jiang, Chinese Patent No. 1528727 (assigned to Zhejiang Univ.); C. A. Radlowski and G. P. Hagen, U. S. Pat. No. 5,095,156 (assigned to Amoco Corp.); C. Y. Tsu and K. L. Yang, Huaxue (1958), (No. 1 ), 39-47; B. N. Dolgov and Yu. N. Volnov, Zhurnal Obshchei Khimii (1993), 3 313-318; M. J. L. Gines and E. Iglesia, J. of Catalysis (1998), 176(1 ), 155-172; T. Tsuchida, AK. Atsumi, S. Sakuma, and T. Inui, US Pat. No. 6,323,383 (assigned to Kabushiki Kaisha Sangi); and GB Pat. No. 381 ,185, assigned to British Industrial Solvents, Ltd. SUMMARY OF THE INVENTION
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.
DETAILS
The present invention relates to a process for making dibutyl ethers from dry ethanol via dry butanol. As used herein, "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. 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. Typically, 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
Base Catalysts (Tanabe, K., in Catalysis: Science and Technology, Anderson, J. and Boudart, M (eds.) 1981 Springer-Verlag, New York) for a description of solid catalysts and how to determine whether a particular catalyst is basic. A suitable base catalyst useful in the current process is either a substance which has the ability to accept protons as defined by Brόnsted, 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. Examples of 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. Commonly used techniques for treatment of supports with metal catalysts can be found in B. C. Gates, Heterogeneous Catalysis, Vol. 2, pp. 1-29, Ed. B. L. Shapiro, Texas A & M University Press, College Station, TX, 1984.
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.
M. N. Dvornikoff and M. W. Farrar, J. of Organic Chemistry (1957), 11 , 540-542, disclose the use of MgO-K2CO3-CuCrO2 catalyst system to promote ethanol condensation to higher alcohols, including 1 -butanol. The disclosed liquid phase reaction using this catalyst showed a 13% conversion of ethanol and 47% selectivity to 1 -butanol.
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. In some embodiments, 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. In one specific embodiment, ethanol is used to produce butanol using a potassium L-type zeolite. J. I. DiCosimo, et al., in Journal of Catalysis (2000), 190(2), 261-275, describe the effect of composition and surface properties on alcohol-coupling reactions using MgxAIOx catalysts for alcohol reactions, including ethanol. Also condensation reactions on MgyAIOx samples involved the formation of a carbanion intermediate on Lewis acid-strong Bronsted base pair sites and yielded products containing a new C-C bond, such as n-C4H8O (or ^C4H9OH) and JSo-C4H8O (or JSO-C4H9OH). They also describe, in Journal of Catalysis (1998), 178(2), 499-510, that the oxidation to acetaldehyde and the aldol condensation to n-butanol both involve initial surface ethoxide formation on a Lewis acid-strong base pair. PCT Publ. No. WO 2006059729 (assigned to Kabushiki Kaisha Sangi) describes a clean process for efficiently producing, from ethanol as a raw material, higher molecular weight alcohols having an even number of carbon atoms, such as 1 -butanol, hexanol and the like. 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(PO4)6(OH)2, tricalcium phosphate Ca3(PO4J2, calcium monohydrogen phosphate CaHPO4 χ(0-2)H2O, calcium diphosphate Ca2P2O7, octacalcium phosphate Ca8H2(PO4)6 χ5H2O, tetracalcium phosphate Ca4(PO4J2O, or amorphous calcium phosphate Ca3(PO4)2 χnH2θ, preferably hydroxyapatite, as a catalyst, the contact time being 0.4 second or longer.
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, 2nd Edition, (1992) Prentice-Hall Inc, CA). Suitable reactors include fixed-bed, adiabatic, fluid-bed, transport bed, and moving bed. During the course of the reaction, 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. An example of 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.
One skilled in the art will know that conditions, such as temperature, catalytic metal, support, reactor configuration and time can affect the reaction kinetics, product yield and product selectivity. Standard experimentation can be used to optimize the yield of 1-butanol from the reaction.
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. See, for example, Solid Acid and Base Catalysts, pages 231-273 (Tanabe, K., in Catalysis: Science and Technology, Anderson, J. and Boudart, M (eds.) 1981 Springer-Verlag, New York) for a description of solid catalysts.
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, 2nd Edition, Chapter 4 (1991 ) McGraw-Hill, New York).
One skilled in the art will know that conditions, such as temperature, catalytic metal, support, reactor configuration and time can affect the reaction kinetics, product yield and product selectivity. Depending on the reaction conditions, such as the particular catalyst used, products other than dibutyl ethers may be produced when 1-butanol is contacted with an acid catalyst. Additional products comprise butenes and isooctenes. Standard experimentation, performed as described in the Examples herein, can be used to optimize the yield of dibutyl ether from the reaction.
Following the reaction, if necessary, 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, 7th 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, 7th Edition, Section 13, 1997, McGraw-Hill, New York). Alternatively, 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. EXAMPLES GENERAL METHODS AND MATERIALS
In the following examples, "C" is degrees Celsius, "mg" is milligram; "ml" is milliliter; "temp" is temperature; "MPa" is mega Pascal; "GC/MS" is gas chromatography/mass spectrometry.
Amberlyst® (manufactured by Rohm and Haas, Philadelphia, PA), tungstic acid, 1-butanol and H2SO4 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®/SiO2 can be obtained from Engelhard; and H-Mordenite can be obtained from Zeolyst Intl. (Valley Forge, PA).
General Procedure for the Conversion of 1-Butanol to Dibutyl Ethers A mixture of 1-butanol and catalyst was contained in a 2 ml vial equipped with a magnetic stir bar. The vial was sealed with a serum cap perforated with a needle to facilitate gas exchange. The vial was placed in a block heater enclosed in a pressure vessel. The vessel was purged with nitrogen and the pressure was set at 6.9 MPa. The block was brought to the indicated temperature and controlled at that temperature for the time indicated. After cooling and venting, the contents of the vial were analyzed by GC/MS using a capillary column (either (a) CP-Wax 58 [Varian; Palo Alto, CA], 25 m X 0.25 mm, 45 C/6 min, 10 C/min up to 200 C, 200 C /10 min, or (b) DB-1701 [J&W (available through Agilent; Palo Alto, CA)], 3O m X 0.2 5mm, 50 C /10 min, 10 C /min up to 250 C, 250 C /2 min). The examples below were performed according to this procedure under the conditions indicated for each example. EXAMPLES 1-13
Reaction of dry 1-butanol (1 -BuOH) with an acid catalyst to produce dibutyl ethers The reactions were carried out for 2 hours at 6.9 MPa of N2.
As those skilled in the art of catalysis know, when working with any catalyst, the reaction conditions need to be optimized. 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).

Claims

CLAIMSWhat is claimed is:
1. 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.
2. The process of Claim 1 , wherein the dry ethanol of step a) is obtained from an ethanol-containing fermentation broth.
EP07867595A 2006-12-01 2007-11-30 Process for making dibutyl ethers from dry ethanol Withdrawn EP2089346A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US87227606P 2006-12-01 2006-12-01
PCT/US2007/024665 WO2008069981A2 (en) 2006-12-01 2007-11-30 Process for making dibutyl ethers from dry ethanol

Publications (1)

Publication Number Publication Date
EP2089346A2 true EP2089346A2 (en) 2009-08-19

Family

ID=39492810

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07867595A Withdrawn EP2089346A2 (en) 2006-12-01 2007-11-30 Process for making dibutyl ethers from dry ethanol

Country Status (6)

Country Link
EP (1) EP2089346A2 (en)
JP (1) JP2010511618A (en)
CN (1) CN101541719A (en)
BR (1) BRPI0717684A2 (en)
CA (1) CA2668877A1 (en)
WO (1) WO2008069981A2 (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11217343A (en) * 1998-01-30 1999-08-10 Sangi Co Ltd Synthesis of chemical industrial feedstock and high-octane fuel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008069981A3 *

Also Published As

Publication number Publication date
CA2668877A1 (en) 2008-06-12
WO2008069981A3 (en) 2008-12-11
BRPI0717684A2 (en) 2013-10-29
WO2008069981A2 (en) 2008-06-12
CN101541719A (en) 2009-09-23
JP2010511618A (en) 2010-04-15

Similar Documents

Publication Publication Date Title
US20100029994A1 (en) Production of butenes and derivatives therefrom from dry ethanol
US20080015397A1 (en) Process for making isooctenes from aqueous 1-butanol
EP2035353A2 (en) Process for making butenes from aqueous 1-butanol
EP2035354A2 (en) Process for making butenes from aqueous isobutanol
EP2066603A2 (en) Process for making butenes from dry 1-butanol
US20090036716A1 (en) Process for making dibutyl ethers from aqueous 1-butanol
US20090023959A1 (en) Process for making dibutyl ethers from dry 1-butanol
US8398728B2 (en) Process for making a composition comprising at least two different dialkyl ethers
US20100174121A1 (en) Production of butenes and derivatives therefrom from dry ethanol
WO2007149396A2 (en) Process for making dibutyl ethers from aqueous isobutanol
US20100036173A1 (en) Production of butenes and derivatives therefrom from aqueous ethanol
EP2129648A2 (en) Process for making dibutyl ethers from dry ethanol
WO2008069981A2 (en) Process for making dibutyl ethers from dry ethanol
WO2008069980A1 (en) Process for making dibutyl ethers from aqueous ethanol
WO2008069982A2 (en) Process for making dibutyl ethers from aqueous ethanol
US20100168478A1 (en) Production of butenes and derivatives therefrom from aqueous ethanol
WO2008069985A1 (en) Production of butenes and derivatives therefrom from aqueous ethanol

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090603

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110601