EP2129647A1 - Process for making dibutyl ethers from aqueous ethanol - Google Patents

Process for making dibutyl ethers from aqueous ethanol

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Publication number
EP2129647A1
EP2129647A1 EP07853208A EP07853208A EP2129647A1 EP 2129647 A1 EP2129647 A1 EP 2129647A1 EP 07853208 A EP07853208 A EP 07853208A EP 07853208 A EP07853208 A EP 07853208A EP 2129647 A1 EP2129647 A1 EP 2129647A1
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EP
European Patent Office
Prior art keywords
ethanol
butanol
reaction product
catalyst
water
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Withdrawn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
EP07853208A
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German (de)
French (fr)
Inventor
Leo Ernest Manzer
Michael B. D'amore
Edward S. Miller
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2129647A1 publication Critical patent/EP2129647A1/en
Withdrawn legal-status Critical Current

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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 aqueous 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.
  • 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.
  • the present invention relates to a process for making dibutyl ethers comprising: a) contacting a reactant comprising aqueous 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 dibutyl ether, and recovering said at least one dibutyl ether from said second reaction product to obtain at least one recovered dibutyl ether.
  • the present invention also relates to a process for making dibutyl ethers, wherein the reactant of step a) above is obtained from an ethanol- containing fermentation broth by a process comprising distilling the fermentation broth to obtain a distillate that comprises ethanol and water, and optionally reducing the water in the distillate to achieve an ethanol concentration in the distillate of between about 50 and about 95 weight percent relative to the weight of the remaining water and ethanol combined.
  • 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 diesel fuels, diesel and jet fuels.
  • the present invention relates to a process for making dibutyl ethers from aqueous 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 aqueous 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. If the first distillation column is insufficient to produce a first overhead stream with a desired ethanol content, then the first overhead stream can be introduced into a second distillation column to produce a second overhead stream, and so on, ultimately leading to the aqueous ethanol (having at least 5% water) required as the reactant in the present invention.
  • aqueous ethanol which may be diluted with an inert gas such as nitrogen and carbon dioxide
  • the stream of aqueous ethanol 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 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 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.
  • 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 1 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.
  • the higher molecular weight alcohols are yielded from ethanol as a starting material with the aid of a calcium phosphate compound, e.g., hydroxyapatite Ca 10 (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 1 or amorphous calcium phosphate Ca 3 (PO 4 ⁇ nH 2 O, preferably hydroxyapatite, as a catalyst, the contact time being 0.4 second or longer.
  • a calcium phosphate compound e.g., hydroxyapatite Ca 10 (PO 4 ) 6 (OH)2, tricalcium phosphate Ca 3 (PO 4 J 2 , calcium monohydrogen phosphate CaHPO 4 ⁇
  • the catalytic conversion of the wet 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.
  • a gas such as, but not limited to, air, steam, hydrogen, nitrogen or combinations thereof
  • 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 phase separation (depending on the product mix) followed by distillation of the organic phase to recover a material whose organic content is predominantly 1-butanol. If the material contains more than 5 weight percent water, the material can be further distilled to reduce the water content to no more than 5 weight percent, thereby producing the partially-purified first reaction product.
  • 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- ⁇ -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 reaction can be carried out in liquid or vapor phase and 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).
  • 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 metal oxides, 5) mixed metal oxides, 6) metal salts such as metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal
  • 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.
  • Sulfated Zirconia was obtained from Engelhard Corporation (Iselin, NJ); 13% Nafion®/SiO 2 can be obtained from Engelhard; and H-Mordenite can be obtained from Zeolyst Intl. (Valley Forge, PA).
  • 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.
  • 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).
  • 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
  • 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).

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Abstract

The present invention relates to processes for making dibutyl ethers using aqueous ethanol optionally obtained from a fermentation broth. The dibutyl ethers so formed find use as additives for fuels, including transportation fuels.

Description

TITLE Process for Making Dibutyl Ethers from Aqueous Ethanol
FIELD OF THE INVENTION The present invention relates to a process for making dibutyl ethers using aqueous 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 dibutyl ethers comprising: a) contacting a reactant comprising aqueous 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 dibutyl ether, and recovering said at least one dibutyl ether from said second reaction product to obtain at least one recovered dibutyl ether.
The present invention also relates to a process for making dibutyl ethers, wherein the reactant of step a) above is obtained from an ethanol- containing fermentation broth by a process comprising distilling the fermentation broth to obtain a distillate that comprises ethanol and water, and optionally reducing the water in the distillate to achieve an ethanol concentration in the distillate of between about 50 and about 95 weight percent relative to the weight of the remaining water and ethanol combined. 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 aqueous 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 aqueous 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. If the first distillation column is insufficient to produce a first overhead stream with a desired ethanol content, then the first overhead stream can be introduced into a second distillation column to produce a second overhead stream, and so on, ultimately leading to the aqueous ethanol (having at least 5% water) required as the reactant in the present invention. These streams, which are vaporous, can be used directly in the current process, or can be condensed and revaporized for use at a later time. The stream of aqueous 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, TX1 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. Dvomikoff 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 MgyAIOx 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 n-C4H9OH) and iso-C4H8O (or iso-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 Ca10(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(PO4J2O1 or amorphous calcium phosphate Ca3(PO4^nH2O, preferably hydroxyapatite, as a catalyst, the contact time being 0.4 second or longer.
The catalytic conversion of the wet 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. 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 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 phase separation (depending on the product mix) followed by distillation of the organic phase to recover a material whose organic content is predominantly 1-butanol. If the material contains more than 5 weight percent water, the material can be further distilled to reduce the water content to no more than 5 weight percent, thereby producing the partially-purified first reaction product.
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-π-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 reaction can be carried out in liquid or vapor phase and 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). 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

CLAIMS What is claimed is:
1. A process for making dibutyl ethers comprising: a) contacting a reactant comprising aqueous 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 dibutyl ether, and recovering said at least one dibutyl ether from said second reaction product to obtain at least one recovered dibutyl ether.
2. The process of Claim 1 , wherein the reactant of step a) is obtained from an ethanol-containing fermentation broth by a process comprising distilling the fermentation broth to obtain a distillate that comprises ethanol and water, and optionally reducing the water in the distillate to achieve an ethanol concentration in the distillate of between about 50 and about 95 weight percent relative to the weight of the remaining water and ethanol combined.
EP07853208A 2006-12-01 2007-11-30 Process for making dibutyl ethers from aqueous ethanol Withdrawn EP2129647A1 (en)

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US5070016A (en) * 1991-03-28 1991-12-03 Revolution Fuels Of America, Inc. Integrated process for producing ethanol, methanol and butyl ethers
US5183947A (en) * 1992-06-19 1993-02-02 Texaco Chemical Company One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified clay catalysts
US5300695A (en) * 1992-12-07 1994-04-05 Amoco Corporation Process for preparing alcohols
US5985100A (en) * 1995-08-30 1999-11-16 Basf Aktiengesellschaft Process for separating butanol and dibutyl ether by means of dual-pressure distillation

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