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WO2013019236A1 - Procédé de récupération d'éthanol dans une colonne de distillation à évacuation latérale - Google Patents

Procédé de récupération d'éthanol dans une colonne de distillation à évacuation latérale Download PDF

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Publication number
WO2013019236A1
WO2013019236A1 PCT/US2011/046503 US2011046503W WO2013019236A1 WO 2013019236 A1 WO2013019236 A1 WO 2013019236A1 US 2011046503 W US2011046503 W US 2011046503W WO 2013019236 A1 WO2013019236 A1 WO 2013019236A1
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WIPO (PCT)
Prior art keywords
ethanol
residue
acetic acid
distillate
column
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Ceased
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PCT/US2011/046503
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English (en)
Inventor
Adam Orosco
Manuel Salado
Lincoln Sarager
R. Jay Warner
Trinity Horton
Victor J. Johnston
David Lee
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Celanese International Corp
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Celanese International Corp
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Priority to PCT/US2011/046503 priority Critical patent/WO2013019236A1/fr
Priority to TW101126178A priority patent/TW201307267A/zh
Publication of WO2013019236A1 publication Critical patent/WO2013019236A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols

Definitions

  • the present invention relates generally to processes for producing alcohol and, in particular, to a process for recovering ethanol from a caide ethanol product comprising ethanol, ethyl acetate, acetic acid and water.
  • Ethanol for industrial use is conventionally produced from petrochemical feed stocks, such as oil, natural gas, or coal, from feed stock intermediates, such as syngas, or from starchy materials or cellulose materials, such as corn or sugar cane.
  • feed stock intermediates such as syngas
  • Conventional methods for producing ethanol from petrochemical feed stocks, as well as from cellulose materials include the acid- catalyzed hydration of ethylene, methanol homologation, direct alcohol synthesis, and Fischer- Tropsch synthesis.
  • Instability in petrochemical feed stock prices contributes to fluctuations in the cost of conventionally produced ethanol, making the need for alternative sources of ethanol production all the greater when feed stock prices rise.
  • Starchy materials, as well as cellulose material are converted to ethanol by fermentation. However, fermentation is typically used for consumer production of ethanol, which is suitable for fuels or human consumption. In addition, fermentation of starchy or cellulose materials competes with food sources and places restraints on the amount of ethanol that can be produced for industrial use.
  • Ethanol production via the reduction of alkanoic acids and/or other carbonyl group- containing compounds has been widely studied, and a variety of combinations of catalysts, supports, and operating conditions have been mentioned in the literature.
  • alkanoic acids e.g., acetic acid
  • other compounds are formed with ethanol or are formed in side reactions.
  • These impurities limit the production and recovery of ethanol from such reaction mixtures.
  • esters are produced that together with ethanol and/or water form azeotropes, which are difficult to separate.
  • acid remains in the caide ethanol product, which must be removed to recover ethanol.
  • EP02060553 describes a process for converting hydrocarbons to ethanol involving converting the hydrocarbons to ethanoic acid and hydrogenating the ethanoic acid to ethanol.
  • the stream from the hydrogenation reactor is separated to obtain an ethanol stream and a stream of acetic acid and ethyl acetate, which is recycled to the hydrogenation reactor.
  • the present invention relates to low energy processes for recovering an alcohol such as ethanol from a caide alcohol product.
  • the invention is a process for producing ethanol comprising hydrogenating acetic acid in a reactor in the presence of a catalyst to form a caide ethanol product. At least a portion of the caide ethanol product is separated in a first distillation column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol, acetic acid and water. A majority of the ethanol in the caide ethanol product that is fed to the first column is removed in the first residue.
  • At least a portion of first residue is separated in a second column to yield a side stream comprising ethanol and a second residue comprising residual acetic acid and/or water.
  • the second column also forms a second distillate for separating residual ethyl acetate from the first residue.
  • the invention is to a process for producing ethanol, comprising: (a) hydrogenating acetic acid in a reactor in the presence of a catalyst to form a caide ethanol product; (b) separating at least a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol; and (c) recovering an ethanol side stream from at least a portion of the first residue in a second column.
  • the second column also preferably forms a second distillate comprising at least 1 wt. % ethyl acetate or at least 5 wt.
  • the process optionally further comprises the step of recycling at least a portion of the second distillate to the reactor.
  • the ethanol side stream preferably comprises at least 50 wt.% ethanol, or at least 88 wt.% ethanol. At least a portion of the first distillate optionally is returned to the reactor.
  • the invention is to a process for producing ethanol, comprising: (a) providing a caide ethanol product comprising ethanol and ethyl acetate (b) separating at least a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol; and (c) recovering an ethanol side stream from at least a portion of the first residue in a second column.
  • the invention is to a process for producing ethanol, comprising hydrogenating acetic acid in a reactor in the presence of a catalyst to form a caide ethanol product; separating a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the caide ethanol product that is fed to the first column is removed in the first residue; and separating at least a portion of first residue in a second column to yield a side stream comprising ethanol and a second residue comprising water and residual acetic acid.
  • at least 70% of the ethanol in the caide ethanol product is removed in the first residue stream.
  • the first residue optionally exits the first distillation column at a temperature from 70 to 155°C.
  • the invention is to a process for producing ethanol, comprising: (a) providing a caide ethanol product; (b) separating a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the caide ethanol product that is fed to the first column is removed in the first residue; and (c) separating at least a portion of first residue in a second column to yield a side stream comprising ethanol and a second residue comprising water and residual acetic acid.
  • the invention is to a process for producing ethanol, comprising: (a) hydrogenating acetic acid in a reactor in the presence of a catalyst to form a caide ethanol product; (b) separating a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the caide ethanol product that is fed to the column is removed in the first residue; and (c) separating at least a portion of first residue in a second column to yield a second distillate comprising residual ethyl acetate and a side stream
  • the invention is to a process for producing ethanol, comprising providing a caide ethanol product comprising ethanol, ethyl acetate, water, and acetic acid; separating a portion of the caide ethanol product in a first column to yield a first distillate comprising ethyl acetate and a first residue comprising ethanol, acetic acid and water, wherein a majority of the ethanol in the caide ethanol product that is fed to the column is removed in the first residue; and separating at least a portion of first residue in a second column to yield a second distillate comprising residual ethyl acetate and a side stream comprising ethanol.
  • the process further comprises the step of hydrolyzing at least a portion of the first distillate in a hydrolysis unit to form a hydrolysis product comprising ethanol and acetic acid, and optionally directing at least a portion of the hydrolysis product to the reactor.
  • the water for the optional hydrolysis step may be derived, for example, from at least in part from the second residue.
  • the resulting first residue may comprise from 10 to 75 wt.% ethanol, from 0.01 to 35 wt.% acetic acid, and from 25 to 70 wt.% water.
  • the first distillate optionally comprises from 10 to 85 wt.% ethyl acetate, from 0.1 to 70 wt.% acetaldehyde, less than 55 wt.% ethanol, and less than 20 wt.% water.
  • the process optionally further comprises reducing the water content of the side stream to yield an ethanol product stream with reduced water content.
  • the process further comprises separating at least a portion of the side stream with a membrane into a permeate stream comprising water and a retentate stream comprising ethanol and less water than the at least a portion of the side stream.
  • the process optionally further comprises extracting at least a portion of the side stream with one or more extractive agents to yield an ethanol product stream with a reduced water content.
  • the resulting side stream may comprise 75 to 96 wt.% ethanol, less than 12 wt.% water, less than 1 wt.% acetic acid, and less than 5 wt.% ethyl acetate.
  • the side stream comprises less than 1 wt.% ethyl acetate and less than 3 wt.% water.
  • the acetic acid is formed from methanol and carbon monoxide, and each of the methanol, the carbon monoxide, and hydrogen for the hydrogenating step is derived from syngas, and the syngas is derived from a carbon source selected from the group consisting of natural gas, oil, petroleum, coal, biomass, and combinations thereof.
  • FIG. 1 is a schematic diagram of an ethanol production system with two separation columns to recover ethanol according to one embodiment of the present invention.
  • the present invention relates to processes for recovering ethanol produced by hydrogenating acetic acid in the presence of a catalyst.
  • the hydrogenation reaction produces a caide ethanol product that comprises ethanol, water, ethyl acetate, acetic acid, and other impurities.
  • the processes of the present invention involve separating the caide ethanol product in a first column into a first residue stream comprising ethanol, water, and acetic acid and a distillate stream comprising ethyl acetate. At least a portion of the first residue stream is separated in a second distillation column to yield a first distillate comprising residual ethyl acetate, an ethanol side stream and a second residue comprising water and residual acetic acid.
  • the ethanol side stream may constitute a salable ethanol composition suitable for many applications, or may be further processed, for example to remove residual water.
  • this separation approach results in reducing energy requirements to recover ethanol from the caide ethanol product.
  • the processes of the present invention use columns, preferably distillation columns.
  • the first residue stream comprises a substantial portion of the ethanol, water, and the acetic acid from the caide ethanol product.
  • the first residue stream may comprise at least 50% of the ethanol from the caide ethanol product, and more preferably at least 70%. In terms of ranges, the residue stream may comprise from 50% to 97.5% of the ethanol from the caide ethanol product, and more preferably from 70% to 99.9%.
  • the amount of ethanol from the caide ethanol recovered in the first residue may be greater than 97.5%, e.g., up to 99.9%, when the ethyl acetate concentration in the caide ethanol product is less than 2 wt.%.
  • taking too much ethanol in the first residue may cause undesirable leakage of ethyl acetate in the residue, although the second column, discussed below, may be able to remove residual ethyl acetate that leaks into the first residue. It is preferred that only a minor amount of ethyl acetate, if any, is withdrawn in the first residue.
  • the first residue comprises ethyl acetate in an amount less than 1000 wppni, less than 100 wppni, less than 50 wppni.
  • the first residue may comprise greater amounts of ethyl acetate since the second column has the ability to remove residual ethyl acetate.
  • the first residue may comprise up to 0.1 wt.% ethyl acetate, up to 0.5 wt.% ethyl acetate or up to 1 wt.% ethyl acetate.
  • the first residue comprises a substantial portion of the water and the acetic acid from the caide ethanol product.
  • the first residue may comprise, for example, at least 80% of the water from the caide ethanol product, and more preferably at least 90%.
  • the first residue preferably comprises from 80% to 99.4% of the water from the caide ethanol product, and more preferably from 90% to 99.4%.
  • the residue stream may comprise at least 85% of the acetic acid from the caide ethanol product, e.g., at least 90% and more preferably about 100%.
  • the residue stream preferably comprises from 85% to 100% of the acetic acid from the caide ethanol product, and more preferably from 90% to 100%.
  • substantially all of the acetic acid is recovered in the residue stream.
  • the first residue which comprise ethanol, water, and acetic acid, may be further separated to recover ethanol.
  • the water and acetic acid may be removed in a second residue in a second column.
  • the energy requirements by the initial column in the process according to the present invention may be less than 5.5 MMBtu per ton of refined ethanol, e.g., less than 4.5 MMBtu per ton of refined ethanol or less than 3.5 MMBtu per ton of refined ethanol.
  • the distillate from the first column may comprise light organics, such as ethyl acetate and acetaldehyde. Removing these components from the caide ethanol product in the first column provides an efficient means for removing light organics. In addition, the light organics are not carried over with the ethanol when multiple columns are used, thus reducing the formation of byproducts that may be formed from the light organics.
  • the light organics are returned to the reactor, where the acetaldehyde and the ethyl acetate may be converted to additional ethanol. Thus, all or a portion of the first distillate may be recycled to the hydrogenation reactor. In some embodiments, the light organics may be separated so that one stream comprising primarily acetaldehyde and/or ethyl acetate is returned to the reactor. In another embodiment, the light organics may be purged from the system.
  • the process of the present invention may be used with any hydrogenation process for producing ethanol.
  • the materials, catalysts, reaction conditions, and separation processes that may be used in the hydrogenation of acetic acid are described further below.
  • the raw materials, acetic acid and hydrogen, used in connection with the process of this invention may be derived from any suitable source including natural gas, petroleum, coal, biomass, and so forth.
  • acetic acid may be produced via methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, and anaerobic fermentation. Methanol carbonylation processes suitable for production of acetic acid are described in U.S. Pat. Nos.
  • some or all of the raw materials for the above-described acetic acid hydrogenation process may be derived partially or entirely from syngas.
  • the acetic acid may be formed from methanol and carbon monoxide, both of which may be derived from syngas.
  • the syngas may be formed by partial oxidation reforming or steam reforming, and the carbon monoxide may be separated from syngas.
  • hydrogen that is used in the step of hydrogenating the acetic acid to form the caide ethanol product may be separated from syngas.
  • the syngas may be derived from variety of carbon sources.
  • the carbon source for example, may be selected from the group consisting of natural gas, oil, petroleum, coal, biomass, and combinations thereof.
  • Syngas or hydrogen may also be obtained from bio-derived methane gas, such as bio-derived methane gas produced by landfills or agricultural waste.
  • the acetic acid used in the hydrogenation step may be formed from the fermentation of biomass.
  • the fermentation process preferably utilizes an acetogenic process or a homoacetogenic microorganism to ferment sugars to acetic acid producing little, if any, carbon dioxide as a by-product.
  • the carbon efficiency for the fermentation process preferably is greater than 70%, greater than 80% or greater than 90% as compared to
  • the microorganism employed in the fermentation process is of a genus selected from the group consisting of Clostridium, Lactobacillus, Moorella, Thermoanaerobacter,
  • Propionibacterium, Propionispera, Anaerobiospirillum, and Bacteriodes and in particular, species selected from the group consisting of Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbaikii, Propionibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum
  • succinicproducens Bacteriodes amylophilus and Bacteriodes aiminicola.
  • all or a portion of the unfermented residue from the biomass, e.g., lignans may be gasified to form hydrogen that may be used in the hydrogenation step of the present invention.
  • Exemplary fermentation processes for forming acetic acid are disclosed in U.S. Pat. Nos. 6,509, 180; 6,927,048; 7,074,603; 7,507,562; 7,351,559; 7,601,865; 7,682,812; and 7,888,082, the entireties of which are incorporated herein by reference. See also US Publ. Nos.
  • biomass examples include, but are not limited to, agricultural wastes, forest products, grasses, and other cellulosic material, timber harvesting residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, niiscanthus, animal manure, municipal garbage, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, plastic, and cloth. See, e.g., U.S. Pat. No. 7,884,253, the entirety of which is incorporated herein by reference.
  • Black liquor a thick, dark liquid that is a byproduct of the Kraft process for transforming wood into pulp, which is then dried to make paper.
  • Black liquor is an aqueous solution of lignin residues, hemicellulose, and inorganic chemicals.
  • U.S. Pat. No. RE 35,377 also incorporated herein by reference, provides a method for the production of methanol by converting carbonaceous materials such as oil, coal, natural gas and biomass materials.
  • the process includes hydrogasification of solid and/or liquid
  • the acetic acid fed to the hydrogenation reaction may also comprise other carboxylic acids and anhydrides, as well as acetaldehyde and acetone.
  • a suitable acetic acid feed stream comprises one or more of the compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof.
  • carboxylic acids such as propanoic acid or its anhydride
  • Water may also be present in the acetic acid feed.
  • acetic acid in vapor form may be taken directly as caide product from the flash vessel of a methanol carbonylation unit of the class described in U.S. Pat. No. 6,657,078, the entirety of which is incorporated herein by reference.
  • the caide vapor product may be fed directly to the ethanol synthesis reaction zones of the present invention without the need for condensing the acetic acid and light ends or removing water, saving overall processing costs.
  • the acetic acid may be vaporized at the reaction temperature, following which the vaporized acetic acid may be fed along with hydrogen in an undiluted state or diluted with a relatively inert carrier gas, such as nitrogen, argon, helium, carbon dioxide and the like.
  • a relatively inert carrier gas such as nitrogen, argon, helium, carbon dioxide and the like.
  • the temperature should be controlled in the system such that it does not fall below the dew point of acetic acid.
  • the acetic acid may be vaporized at the boiling point of acetic acid at the particular pressure, and then the vaporized acetic acid may be further heated to the reactor inlet temperature.
  • the acetic acid is mixed with other gases before vaporizing, followed by heating the mixed vapors up to the reactor inlet temperature.
  • the acetic acid is transferred to the vapor state by passing hydrogen and/or recycle gas through the acetic acid at a temperature at or below 125°C, followed by heating of the combined gaseous stream to the
  • Some embodiments of the process of hydrogenating acetic acid to form ethanol may include a variety of configurations using a fixed bed reactor or a fluidized bed reactor.
  • an "adiabatic" reactor can be used; that is, there is little or no need for internal plumbing through the reaction zone to add or remove heat.
  • a radial flow reactor or reactors may be employed, or a series of reactors may be employed with or without heat exchange, quenching, or introduction of additional feed material.
  • a shell and tube reactor provided with a heat transfer medium may be used.
  • the reaction zone may be housed in a single vessel or in a series of vessels with heat exchangers therebetween.
  • the catalyst is employed in a fixed bed reactor, e.g., in the shape of a pipe or tube, where the reactants, typically in the vapor form, are passed over or through the catalyst.
  • a fixed bed reactor e.g., in the shape of a pipe or tube
  • Other reactors such as fluid or ebullient bed reactors, can be employed.
  • the hydrogenation catalysts may be used in conjunction with an inert material to regulate the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant compounds with the catalyst particles.
  • the hydrogenation reaction may be carried out in either the liquid phase or vapor phase.
  • the reaction is carried out in the vapor phase under the following conditions.
  • the reaction temperature may range from 125°C to 350°C, e.g., from 200°C to 325°C, from 225°C to 300°C, or from 250°C to 300°C.
  • the pressure may range from 10 kPa to 3000 kPa, e.g., from 50 kPa to 2300 kPa, or from 100 kPa to 1500 kPa.
  • the reactants may be fed to the reactor at a gas hourly space velocity (GHSV) of greater than 500 hr “1 , e.g., greater than 1000 hr “1 , greater than 2500 hr “1 or even greater than 5000 hr “1 .
  • GHSV gas hourly space velocity
  • the GHSV may range from 50 hr “1 to 50,000 hr “1 , e.g., from 500 hr "1 to 30,000 hr “1 , from 1000 hr "1 to 10,000 hr "1 , or from 1000 hr “1 to 6500 hr “1 .
  • the hydrogenation optionally is carried out at a pressure just sufficient to overcome the pressure drop across the catalytic bed at the GHSV selected, although there is no bar to the use of higher pressures, it being understood that considerable pressure drop through the reactor bed may be experienced at high space velocities, e.g., 5000 hr "1 or 6,500 hr "1 .
  • the reaction consumes two moles of hydrogen per mole of acetic acid to produce one mole of ethanol
  • the actual molar ratio of hydrogen to acetic acid in the feed stream may vary from about 100: 1 to 1 : 100, e.g., from 50: 1 to 1 :50, from 20: 1 to 1 :2, or from 12: 1 to 1 : 1.
  • the molar ratio of hydrogen to acetic acid is greater than 2: 1, e.g., greater than 4: 1 or greater than 8: 1.
  • Contact or residence time can also vary widely, depending upon such variables as amount of acetic acid, catalyst, reactor, temperature, and pressure. Typical contact times range from a fraction of a second to more than several hours when a catalyst system other than a fixed bed is used, with preferred contact times, at least for vapor phase reactions, of from 0.1 to 100 seconds, e.g., from 0.3 to 80 seconds or from 0.4 to 30 seconds.
  • the hydrogenation of acetic acid to form ethanol is preferably conducted in the presence of a hydrogenation catalyst.
  • Suitable hydrogenation catalysts include catalysts comprising a first metal and optionally one or more of a second metal, a third metal or any number of additional metals, optionally on a catalyst support.
  • the first and optional second and third metals may be selected from Group IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII transition metals, a lanthanide metal, an actinide metal or a metal selected from any of Groups IIIA, IV A, VA, and VIA.
  • Preferred metal combinations for some exemplary catalyst compositions include platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/aithenium, cobalt/tin,
  • the catalyst comprises a Co/Mo/S catalyst of the type described in U.S. Pub. No. 2009/0069609, the entirety of which is incorporated herein by reference.
  • the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten.
  • the first metal is selected from the group consisting of platinum, palladium, cobalt, nickel, and ruthenium. More preferably, the first metal is selected from platinum and palladium.
  • the catalyst comprises platinum in an amount less than 5 wt.%, e.g., less than 3 wt.% or less than 1 wt.%, due to the high commercial demand for platinum.
  • the catalyst further comprises a second metal, which typically would function as a promoter.
  • the second metal preferably is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel. More preferably, the second metal is selected from the group consisting of copper, tin, cobalt, rhenium, and nickel. More preferably, the second metal is selected from tin and rhenium.
  • the first metal is present in the catalyst in an amount from 0.1 to 10 wt.%, e.g., from 0.1 to 5 wt.%, or from 0.1 to 3 wt.%.
  • the second metal preferably is present in an amount from 0.1 to 20 wt.%, e.g., from 0.1 to 10 wt.%, or from 0.1 to 5 wt.%.
  • the two or more metals may be alloyed with one another or may comprise a non-alloyed metal solution or mixture.
  • the preferred metal ratios may vary depending on the metals used in the catalyst.
  • the mole ratio of the first metal to the second metal is from 10: 1 to 1 : 10, e.g., from 4: 1 to 1 :4, from 2: 1 to 1 :2, from 1.5: 1 to 1 : 1.5 or from 1.1 : 1 to 1 : 1.1.
  • the catalyst may also comprise a third metal selected from any of the metals listed above in connection with the first or second metal, so long as the third metal is different from the first and second metals.
  • the third metal is selected from the group consisting of cobalt, palladium, aithenium, copper, zinc, platinum, tin, and rhenium. More preferably, the third metal is selected from cobalt, palladium, and aithenium.
  • the total weight of the third metal preferably is from 0.05 to 4 wt.%, e.g., from 0.1 to 3 wt.%, or from 0.1 to 2 wt.%.
  • the catalysts further comprise a support or a modified support.
  • modified support refers to a support that includes a support material and a support modifier, which adjusts the acidity of the support material.
  • the total weight of the support or modified support based on the total weight of the catalyst, preferably is from 75 to 99.9 wt.%, e.g., from 78 to 97 wt.%, or from 80 to 95 wt.%.
  • the support modifier is present in an amount from 0.1 to 50 wt.%, e.g., from 0.2 to 25 wt.%, from 0.5 to 15 wt.%, or from 1 to 8 wt.%, based on the total weight of the catalyst.
  • the metals of the catalysts may be dispersed
  • support materials are selected such that the catalyst system is suitably active, selective and robust under the process conditions employed for the formation of ethanol.
  • Suitable support materials may include, for example, stable metal oxide-based supports or ceramic-based supports.
  • Preferred supports include silicaceous supports, such as silica, silica/alumina, a Group DA silicate such as calcium metasilicate, pyrogenic silica, high purity silica, and mixtures thereof.
  • Other supports may include, but are not limited to, iron oxide, alumina, titania, zirconia, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbons, and mixtures thereof.
  • the catalyst support may be modified with a support modifier.
  • the support modifier may be an acidic modifier that increases the acidity of the catalyst.
  • Suitable acidic support modifiers may be selected from the group consisting of: oxides of Group IVB metals, oxides of Group VB metals, oxides of Group VIB metals, oxides of Group VIIB metals, oxides of Group VIIIB metals, aluminum oxides, and mixtures thereof.
  • Acidic support modifiers include those selected from the group consisting of Ti0 2 , Zr0 2 , Nb 2 Os, Ta 2 Os, Al 2 0_3, B 2 0 3 , P 2 Os, and Sb 2 0_3.
  • Preferred acidic support modifiers include those selected from the group consisting of Ti0 2 , Zr0 2 , Nb 2 Os, Ta 2 Os, and Al 2 03.
  • the acidic modifier may also include W0 3 , Mo0 3 , Fe 2 0 3 , Cr 2 0 3 , V 2 0 5 , Mn0 2 , CuO, Co 2 0 3 , and Bi 2 0 3 .
  • the support modifier may be a basic modifier that has a low volatility or no volatility.
  • Such basic modifiers may be selected from the group consisting of: (i) alkaline earth oxides, (ii) alkali metal oxides, (iii) alkaline earth metal iiietasilicates, (iv) alkali metal iiietasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal iiietasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal iiietasilicates, and mixtures thereof.
  • the support modifier is selected from the group consisting of oxides and iiietasilicates of any of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, as well as mixtures of any of the foregoing. More preferably, the basic support modifier is a calcium silicate, and even more preferably calcium metasilicate (CaSi0 3 ). If the basic support modifier comprises calcium metasilicate, it is preferred that at least a portion of the calcium metasilicate is in crystalline form.
  • a preferred silica support material is SS61 138 High Surface Area (HSA) Silica Catalyst Carrier from Saint Gobain NorPro.
  • the Saint-Gobain NorPro SS61 138 silica exhibits the following properties: contains approximately 95 wt.% high surface area silica; surface area of about 250 m 2 /g; median pore diameter of about 12 nni; average pore volume of about 1.0 cm 3 /g as measured by mercury intaision porosimetry and a packing density of about 0.352 g/ciii 3 (22 lb/ft 3 ).
  • a preferred silica/alumina support material is KA- 160 silica spheres from Sud Cheniie having a nominal diameter of about 5 mm, a density of about 0.562 g/nil, an absorptivity of about 0.583 g H 2 0/g support, a surface area of about 160 to 175 m 2 /g, and a pore volume of about 0.68 nil/g.
  • the catalyst compositions suitable for use with the present invention preferably are formed through metal impregnation of the modified support, although other processes such as chemical vapor deposition may also be employed. Such impregnation techniques are described in U.S. Pat. Nos. 7,608,744 and 7,863,489 and U.S. Pub. No. 2010/0197485 referred to above, the entireties of which are incorporated herein by reference.
  • the hydrogenation of acetic acid may achieve favorable conversion of acetic acid and favorable selectivity and productivity to ethanol.
  • conversion refers to the amount of acetic acid in the feed that is converted to a compound other than acetic acid. Conversion is expressed as a mole percentage based on acetic acid in the feed. The conversion may be at least 10%, e.g., at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.
  • catalysts that have high conversions are desirable, such as at least 80% or at least 90%, in some embodiments a low conversion may be acceptable at high selectivity for ethanol. It is, of course, well understood that in many cases, it is possible to compensate for conversion by appropriate recycle streams or use of larger reactors, but it is more difficult to compensate for poor selectivity.
  • Selectivity is expressed as a mole percent based on converted acetic acid. It should be understood that each compound converted from acetic acid has an independent selectivity and that selectivity is independent from conversion. For example, if 60 mole % of the converted acetic acid is converted to ethanol, we refer to the ethanol selectivity as 60%.
  • the catalyst selectivity to ethoxylates is at least 60%, e.g., at least 70%, or at least 80%.
  • the term "ethoxylates" refers specifically to the compounds ethanol, acetaldehyde, and ethyl acetate.
  • the selectivity to ethanol is at least 80%, e.g., at least 85% or at least 88%.
  • Preferred embodiments of the hydrogenation process also have low selectivity to undesirable products, such as methane, ethane, and carbon dioxide.
  • the selectivity to these undesirable products preferably is less than 4%, e.g., less than 2% or less than 1%. More preferably, these undesirable products are present in undetectable amounts.
  • Formation of alkanes may be low, and ideally less than 2%, less than 1%, or less than 0.5% of the acetic acid passed over the catalyst is converted to alkanes, which have little value other than as fuel.
  • productivity refers to the grams of a specified product, e.g., ethanol, formed during the hydrogenation based on the kilograms of catalyst used per hour.
  • the productivity preferably is from 100 to 3,000 grams of ethanol per kilogram of catalyst per hour, e.g., from 400 to 2,500 grams of ethanol per kilogram of catalyst per hour or from 600 to 2,000 grams of ethanol per kilogram of catalyst per hour.
  • Operating under the conditions of the present invention may result in ethanol production on the order of at least 0.1 tons of ethanol per hour, e.g., at least 1 ton of ethanol per hour, at least 5 tons of ethanol per hour, or at least 10 tons of ethanol per hour.
  • Larger scale industrial production of ethanol depending on the scale, generally should be at least 1 ton of ethanol per hour, e.g., at least 15 tons of ethanol per hour or at least 30 tons of ethanol per hour.
  • the process of the present invention may produce from 0.1 to 160 tons of ethanol per hour, e.g., from 15 to 160 tons of ethanol per hour or from 30 to 80 tons of ethanol per hour.
  • the caide ethanol product produced by the hydrogenation process, before any subsequent processing, such as purification and separation will typically comprise acetic acid, ethanol and water.
  • the term "caide ethanol product” refers to any composition comprising from 5 to 70 wt.% ethanol and from 5 to 40 wt.% water.
  • Exemplary compositional ranges for the caide ethanol product are provided in Table 1.
  • the "others” identified in Table 1 may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide.
  • the caide ethanol product comprises acetic acid in an amount less than 20 wt.%, e.g., less than 15 wt. %, less than 10 wt.% or less than 5 wt.%.
  • the conversion of acetic acid is preferably greater than 75%, e.g., greater than 85% or greater than 90%.
  • the selectivity to ethanol may also be preferably high, and is preferably greater than 75%, e.g., greater than 85% or greater than 90%.
  • Hydrogenation system 100 provides a suitable hydrogenation reactor and a process for separating ethanol from the caide reaction mixture according to an embodiment of the invention.
  • System 100 comprises reaction zone 101 and separation zone 102.
  • Reaction zone 101 comprises reactor 103, hydrogen feed line 104 and acetic acid feed line 105.
  • Separation zone 102 comprises a separator 106, e.g., a flash vessel, and distillation columns.
  • Hydrogen and an akanoic acid are fed to a vaporizer 109 via lines 104 and 105, respectively, to create a vapor feed stream in line 1 10 that is directed to reactor 103.
  • lines 104 and 105 may be combined and jointly fed to the vaporizer 109.
  • the temperature of the vapor feed stream in line 1 10 is preferably from 100°C to 350°C, e.g., from 120°C to 310°C or from 150°C to 300°C. Any feed that is not vaporized is removed from vaporizer 109, and may be recycled or discarded.
  • Reactor 103 contains the catalyst that is used in the hydrogenation of the alkanoic acid, preferably acetic acid.
  • one or more guard beds may be used upstream of the reactor, optionally upstream of vaporizer 109, to protect the catalyst from poisons or undesirable impurities contained in the feed or return/recycle streams. Such guard beds may be employed in the vapor or liquid streams. Suitable guard bed materials may include, for example, carbon, silica, alumina, ceramic, or resins.
  • the guard bed media is functionalized, e.g., silver functionalized, to trap particular species such as sulfur or halogens.
  • a caide ethanol product stream is withdrawn, preferably continuously, from reactor 103 via line 1 1 1.
  • the caide ethanol product stream may be condensed and fed to a separator 106, which, in turn, forms a vapor stream 1 12 and a liquid stream 1 13.
  • separator 106 may comprise a flasher or a knockout pot.
  • the separator 106 may operate at a temperature of from 20°C to 250°C, e.g., from 30°C to 225°C or from 60°C to 200°C.
  • the pressure of separator 106 may be from 50 kPa to 2000 kPa, e.g., from 75 kPa to 1500 kPa or from 100 kPa to 1000 kPa.
  • the caide ethanol product in line 1 1 1 may pass through one or more membranes to separate hydrogen and/or other non-condensable gases.
  • the vapor stream 1 12 exiting separator 106 may comprise hydrogen and hydrocarbons, and may be purged and/or returned to reaction zone 101. As shown, vapor stream 1 12 is combined with the hydrogen feed 104 and co-fed to vaporizer 109. In some embodiments, the returned vapor stream 1 12 may be compressed before being combined with hydrogen feed 104.
  • liquid stream 1 13 from separator 106 is withdrawn and directed as a feed composition to the side of first distillation column 107, also referred to as a "light ends column.”
  • the contents of liquid stream 1 13 are substantially similar to the caide ethanol product obtained from the reactor, except that the composition has been depleted of hydrogen, carbon dioxide, methane or ethane, which have been removed by separator 106.
  • liquid stream 1 13 may also be referred to as a caide ethanol product.
  • Exemplary components of liquid stream 1 13 are provided in Table 2. It should be understood that liquid stream 1 13 may contain other components, not listed in Table 2, such as components derived from the feed. TABLE 2
  • the "other esters” in Table 2 may include, but are not limited to, ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate or mixtures thereof.
  • the "other ethers” in Table 2 may include, but are not limited to, diethyl ether, methyl ethyl ether, isobutyl ethyl ether or mixtures thereof.
  • the "other alcohols” in Table 2 may include, but are not limited to, methanol, isopropanol, n-propanol, n-butanol or mixtures thereof. In one
  • liquid stream 1 13 may comprise propanol, e.g., isopropanol and/or n-propanol, in an amount from 0.001 to 0.1 wt.%, from 0.001 to 0.05 wt.% or from 0.001 to 0.03 wt.%.
  • propanol e.g., isopropanol and/or n-propanol
  • these other components may be carried through in any of the distillate or residue streams described herein and will not be further described herein, unless indicated otherwise.
  • caide ethanol product in line 1 1 1 or in liquid stream 1 13 may be further fed to an esterification reactor, hydrogenolysis reactor, or combination thereof.
  • An esterification reactor may be used to consume acetic acid present in the caide ethanol product to further reduce the amount of acetic acid to be removed.
  • Hydrogenolysis may be used to convert ethyl acetate in the caide ethanol product to ethanol.
  • liquid stream 1 13 is introduced in the upper part of first column 107, e.g., upper half or upper third. In one embodiment, no entrainers are added to first column 107.
  • first column 107 a weight majority of the ethanol, water, acetic acid, and other heavy components, if present, are removed from liquid stream 1 13 and are withdrawn, preferably continuously, as residue in line 1 14.
  • First column 107 also forms an overhead distillate, which is withdrawn in line 1 15, and which may be condensed and refluxed, for example, at a ratio of from 30: 1 to 1 :30, e.g., from 10: 1 to 1 : 10 or from 1 :5 to 5: 1.
  • the overhead distillate in stream 1 15 preferably comprises a weight majority of the ethyl acetate and acetaldehyde from liquid stream 1 13.
  • a small amount e.g., at least 0.1 wppni, at least 1 wppni, at least 10 wppni, at least 100 wppni or at least 1000 wppni, of ethyl acetate and/or acetaldehyde, separately or collectively, may be permitted to pass into the first residue since the second column, discussed below, provides a means for effectively removing residual amounts of these compounds from the product alcohol composition.
  • the temperature of the residue exiting in line 1 14 preferably is from 70°C to 155°C, e.g., from 90°C to 130°C or from 100°C to 1 10°C.
  • the base of column 107 may be maintained at a relatively low temperature by withdrawing a residue stream comprising ethanol, water, and acetic acid, thereby providing an energy efficiency advantage.
  • the temperature of the distillate exiting in line 1 15 from column 107 preferably at 170 kPa is from 75°C to 100°C, e.g., from 75°C to 83°C or from 81°C to 84°C.
  • the pressure of first column 107 may range from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa.
  • Exemplary components of the distillate and residue compositions for first column 107 are provided in Table 3 below. It should also be understood that the distillate and residue may also contain other components, not listed in Table 3.
  • distillate and residue of the first column may also be referred to as the "first distillate” or “first residue.”
  • first distillate or “first residue.”
  • second, third, etc. similar numeric modifiers
  • Acetic Acid 0.01 to 35 0.1 to 30 0.2 to 25
  • column 107 may be operated at a temperature where most of the water, ethanol, and acetic acid are removed from the residue stream and only a small amount of ethanol and water is collected in the distillate stream due to the formation of binary and tertiary azeotropes.
  • the weight ratio of water in the residue in line 1 14 to water in the distillate in line 1 15 may be greater than 1 : 1, e.g., greater than 2: 1.
  • the weight ratio of ethanol in the residue to ethanol in the distillate may be greater than 1 : 1, e.g., greater than 2: 1.
  • the weight ratio of ethyl acetate in the first distillate in line 1 15 to ethyl acetate in the first residue in line 1 14 may be greater than 1 : 1, e.g., greater than 2: 1.
  • the weight ratio of acetaldehyde in the first distillate in line 1 15 to acetaldehyde in the first residue in line 1 14 may be greater than 1 : 1, e.g., greater than 2: 1.
  • the amount of acetic acid in the first residue 1 14 may vary depending primarily on the conversion in reactor 103. In one embodiment, when the conversion is high, e.g., greater than 90%, the amount of acetic acid in the first residue may be less than 10 wt.%, e.g., less than 5 wt.% or less than 2 wt.%. In other embodiments, when the conversion is lower, e.g., less than 90%, the amount of acetic acid in the first residue may be greater than 10 wt.%.
  • the separation in first column 107 may be conducted with or without the addition of an azeotrope or extractive agent.
  • the first distillate preferably is substantially free of acetic acid, e.g., comprising less than 1000 ppni, less than 500 ppni or less than 100 ppni acetic acid.
  • the distillate may be purged from the system or recycled in whole or part to reactor 103.
  • the distillate may be further separated, e.g., in a distillation column (not shown), into an
  • acetaldehyde stream and an ethyl acetate stream. Either of these streams may be returned to the reactor 103 or separated from system 100 as a separate product.
  • all or a portion of the first distillate is directed to a hydrolysis unit in which the ethyl acetate contained therein is reacted with water to form ethanol and acetic acid, both of which may be recycled to the reactor or sent to the separation system for recovery.
  • the process includes the step of hydrolyzing at least a portion of the first distillate in a hydrolysis unit to form a hydrolysis product comprising ethanol and acetic acid and directing at least a portion of the hydrolysis product to the reactor or separation system, e.g., to the first column or the second column.
  • all or a portion of the first distillate is recycled to the reactor without hydrolysis.
  • Some species such as acetals, may decompose in first column 107 such that very low amounts, or even no detectable amounts, of acetals remain in the distillate or residue.
  • an equilibrium reaction between acetic acid/ethanol and ethyl acetate may occur in the caide ethanol product after it exits reactor 103. Depending on the concentration of acetic acid in the caide ethanol product, this equilibrium may be driven toward formation of ethyl acetate. This reaction may be regulated through the residence time and/or temperature of the caide ethanol product.
  • the columns shown in FIG. 1 may comprise any distillation column capable of performing the desired separation and/or purification.
  • Each column preferably comprises a tray column having from 1 to 150 trays, e.g., from 10 to 100 trays, from 20 to 95 trays or from 30 to 75 trays.
  • the trays may be sieve trays, fixed valve trays, movable valve trays, or any other suitable design known in the art.
  • a packed column may be used.
  • staictured packing or random packing may be employed.
  • the trays or packing may be arranged in one continuous column or they may be arranged in two or more columns such that the vapor from the first section enters the second section while the liquid from the second section enters the first section, etc.
  • the associated condensers and liquid separation vessels that may be employed with each of the distillation columns may be of any conventional design and are simplified in the figures.
  • Heat may be supplied to the base of each column or to a circulating bottom stream through a heat exchanger or reboiler.
  • Other types of reboilers such as internal reboilers, may also be used.
  • the heat that is provided to the reboilers may be derived from any heat generated during the process that is integrated with the reboilers or from an external source such as another heat generating chemical process or a boiler.
  • one reactor and one flasher are shown in the figures, additional reactors, flashers, condensers, heating elements, and other components may be used in various embodiments of the present invention.
  • temperatures and pressures employed in the columns may vary. As a practical matter, pressures from 10 kPa to 3000 kPa will generally be employed in these zones although in some embodiments subatmospheric pressures or superatmospheric pressures may be employed. Temperatures within the various zones will normally range between the boiling points of the composition removed as the distillate and the composition removed as the residue. As will be recognized by those skilled in the art, the temperature at a given location in an operating distillation column is dependent on the composition of the material at that location and the pressure of column. In addition, feed rates may vary depending on the size of the production process and, if described, may be generically referred to in terms of feed weight ratios.
  • the residue in line 1 14 may be further separated depending on the concentration of acetic acid, water and/or ethyl acetate.
  • residue in line 1 14 is further separated in a second column 1 19.
  • the second column 1 19 is referred to as an "acid separation column," because the second residue 122 comprises acetic acid and water.
  • An acid separation column may be used, for example, when the acetic acid concentration in the first residue is greater than 1 wt.%, e.g., greater than 5 wt.%.
  • the first residue in line 1 14 is introduced to second column 1 19, e.g., acid separation column, preferably in the top part of column 108, e.g., top half or top third.
  • Second column 1 19 yields a second residue in line 122 comprising acetic acid and water, a second distillate in line 120 comprising residual ethyl acetate and/or residual acetaldehyde, and an ethanol side stream 121 comprising ethanol.
  • the present invention provides a low energy solution, optionally having only two columns, for recovering ethanol from a caide ethanol product.
  • Second column 108 may be a tray column or packed column.
  • second column 108 is a tray column having from 5 to 150 trays, e.g., from 15 to 50 trays or from 20 to 45 trays.
  • the temperature and pressure of second column 1 19 may vary, when at atmospheric pressure the temperature of the second residue exiting in line 122 from second column 1 19 preferably is from 95°C to 130°C, e.g., from 100°C to 125°C or from 1 10°C to 120°C.
  • the temperature of the second distillate exiting in line 120 from second column 1 19 preferably is from 60°C to 105°C, e.g., from 75°C to 100°C or from 80°C to 100°C.
  • the temperature of the ethanol side stream exiting in line 121 preferably is from 60°C to 105°C, e.g., from 75°C to 100°C or from 80°C to 100°C.
  • the pressure of second column 1 19 may range from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa.
  • Exemplary components for the distillate and residue compositions for second column 1 19 are provided in Table 4 below. It should be understood that the distillate and residue may also contain other components, not listed in Table 4, such as components derived from the feed.
  • Acetic Acid ⁇ 0.5 ⁇ 0.01 0.001 to 0.01
  • the ratio of ethanol in the side stream in line 121 to ethanol in the second residue in line 122 preferably is at least 2: 1, at least 10: 1 or at least 35: 1.
  • the ratio of water in the second residue 122 to water in the second distillate 120 is greater than 2: 1, e.g., greater than 4: 1 or greater than 6: 1.
  • the ratio of acetic acid in the second residue 122 to acetic acid in the second distillate 120 preferably is greater than 10: 1, e.g., greater than 15: 1 or greater than 20: 1.
  • the second distillate in line 120 and the side stream 121 are substantially free of acetic acid and may only contain, if any, trace amounts of acetic acid.
  • a reduced concentration of acetic acid in lines 120, 121 advantageously provides an ethanol product that also has no amount or a trace amount of acetic acid.
  • an advantage of the present separation scheme is the ability to effectively remove ethyl acetate from product ethanol in a two column system.
  • the ratio of ethyl acetate in the second distillate in line 120 to ethyl acetate in the side stream in line 121 is greater than 2: 1, greater than 5 : 1 or greater than 10: 1.
  • the second distillate in line 1 18 may be purged from system or recycled in whole or part to reactor 103, along with first distillate in line 1 15.
  • the second residue in line 122 comprises acetic acid and water. Depending on the amount of water and acetic acid contained in the second residue, the residue may be treated in one or more of the following processes. The following are exemplary processes for further treating the residue and it should be understood that any (or none) of the following may be used regardless of acid concentration. When the residue comprises in large part acetic acid, e.g., greater than 70 wt.%, the residue may be recycled to the reactor without any separation of the water.
  • the residue may be separated into an acetic acid stream and a water stream when the residue comprises a majority of acetic acid, e.g., greater than 50 wt.%.
  • Acetic acid may also be recovered in some embodiments from the residue having a lower acid concentration.
  • the residue may be separated into the acetic acid and water streams by a distillation column or one or more membranes. If a membrane or an array of membranes is employed to separate the acetic acid from the water, the membrane or array of membranes may be selected from any suitable acid resistant membrane that is capable of removing a permeate water stream.
  • the resulting acetic acid stream comprising acetic acid optionally is returned to the reaction zone.
  • the resulting water stream may be used as an extractive agent or to hydrolyze an ester-containing stream in a hydrolysis unit, e.g., to hydrolyze all or a portion of first distillate 1 15, as discussed above.
  • possible options include one or more of: (i) returning a portion of the residue to reactor 103, (ii) neutralizing the acid, (iii) reacting the acid with an alcohol, or (iv) disposing of the residue in a waste water treatment facility. It also may be possible to separate a residue comprising less than 50 wt.% acetic acid using a weak acid recovery distillation column to which a solvent (optionally acting as an azeotroping agent) may be added.
  • Exemplary solvents that may be suitable for this purpose include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, vinyl acetate, diisopropyl ether, carbon disulfide, tetrahydrofuran, isopropanol, ethanol, and C3-C 12 alkanes.
  • the residue comprises less than 10 wt.% acetic acid.
  • the acetic acid may be neutralized with any suitable alkali or alkaline earth metal base, such as sodium hydroxide or potassium hydroxide.
  • the residue comprises less than 50 wt.% acid.
  • the alcohol may be any suitable alcohol, such as methanol, ethanol, propanol, butanol, or mixtures thereof.
  • the reaction forms an ester that may be integrated with other systems, such as carbonylation production or an ester production process.
  • the alcohol comprises ethanol and the resulting ester comprises ethyl acetate.
  • the resulting ester may be fed to the hydrogenation reactor.
  • the second residue when the second residue comprises very minor amounts of acetic acid, e.g., less than 5 wt.%, the second residue may be disposed of to a waste water treatment facility without further processing.
  • the organic content, e.g., acetic acid content, of the residue beneficially may be suitable to feed microorganisms used in a waste water treatment facility.
  • the ethanol product may be derived from the side stream in line 121.
  • the side stream in line 121 comprises at least 88 wt.% ethanol, at least 90 wt.% ethanol, at least 95 wt.% ethanol or at least 97 wt.% ethanol.
  • the side stream in line 121 may comprise from 75 to 96 wt.% ethanol and less than 12 wt.% water.
  • the amount of water in the side stream of line 121 may be closer to the azeotropic amount of water, e.g., at least 4 wt.%, preferably less than 20 wt.%, e.g., less than 12 wt.% or less than 7.5 wt.%.
  • Water optionally may be removed from the side stream in line 121 using several different separation techniques. Residual water removal may be accomplished, for example, using one or more adsorption units, membranes, molecular sieves, extractive distillation units, or a combination thereof. Suitable adsorption units include pressure swing adsorption systems and thermal swing adsorption units. Particularly preferred techniques include the use of distillation column, membranes, adsorption units and combinations thereof. For example, the side stream from the second column may be distilled in an additional distillation column to form an additional distillate comprising ethanol and an additional residue comprising water.
  • an adsorption unit 123 may be provided to remove water in water stream 125 from the side stream in line 121 thus producing an anhydrous ethanol stream 124, preferably comprising 97 wt.% or more ethanol, e.g., at least 98 wt.% ethanol or at least 99.5 wt.% ethanol.
  • the adsorption unit 123 may employ a suitable adsorption agent such as a zeolite.
  • adsorption unit 123 is a pressure swing adsorption (PSA) unit that is operated at a temperature from 30°C to 160°C, e.g., from 80°C to 140°C, and a pressure of from 0.01 kPa to 550 kPa, e.g., from 1 to 150 kPa.
  • the PSA unit may comprise two to five beds.
  • Adsorption unit 123 may remove at least 95% of the water from the side stream in line 121, and more preferably from 95% to 99.9% of the water from the side stream in line 121.
  • Water stream 125 may be combined with any other water stream from system 100 and may be removed from the system or used elsewhere in the system, for example, as a hydrolyzing agent for the hydrolysis of ethyl acetate in the first distillate.
  • the water stream may also comprise ethanol, in which case it may be desirable to feed all or a portion of the water stream back to first column 107 or other separation device for further ethanol recovery.
  • the ethanol product produced by the process of the present invention may be an industrial grade ethanol comprising from 75 to 96 wt.% ethanol, e.g., from 80 to 96 wt.% or from 85 to 96 wt.% ethanol, based on the total weight of the ethanol product.
  • Exemplary finished ethanol compositional ranges are provided below in Table 5.
  • the finished ethanol composition of the present invention preferably contains very low amounts, e.g., less than 0.5 wt.%, of other alcohols, such as methanol, butanol, isobutanol, isoamyl alcohol and other C 4 -C 20 alcohols.
  • the amount of isopropanol in the finished ethanol composition is from 80 to 1,000 wppni, e.g., from 95 to 1,000 wppni, from 100 to 700 wppni, or from 150 to 500 wppni.
  • the finished ethanol composition is substantially free of acetaldehyde, optionally comprising less than 8 wppni acetaldehyde, e.g., less than 5 wppni or less than 1 wppni.
  • the finished ethanol composition produced by the embodiments of the present invention may be used in a variety of applications including applications as fuels, solvents, chemical feedstocks, pharmaceutical products, cleansers, sanitizers, hydrogenation transport or consumption. In fuel applications, the finished ethanol composition may be blended with gasoline for motor vehicles such as automobiles, boats and small piston engine aircraft.
  • the finished ethanol composition may be used as a solvent for toiletry and cosmetic preparations, detergents, disinfectants, coatings, inks, and pharmaceuticals.
  • the finished ethanol composition may also be used as a processing solvent in manufacturing processes for medicinal products, food preparations, dyes, photocheiiiicals and latex processing.
  • the finished ethanol composition may also be used as a chemical feedstock to make other chemicals such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers,
  • the finished ethanol composition may be esterified with acetic acid.
  • the finished ethanol composition may be dehydrated to produce ethylene.
  • Any known dehydration catalyst can be employed to dehydrate ethanol, such as those described in copending U.S. Pub. Nos. 2010/0030002 and 2010/0030001, the entireties of which are incorporated herein by reference.
  • a zeolite catalyst for example, may be employed as the dehydration catalyst.
  • the zeolite has a pore diameter of at least about 0.6 nni
  • preferred zeolites include dehydration catalysts selected from the group consisting of mordenites, ZSM-5, a zeolite X and a zeolite Y.
  • Zeolite X is described, for example, in U.S. Pat. No.

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Abstract

La présente invention a pour objet la récupération d'un alcool comme l'éthanol à partir d'un produit alcoolique brut, obtenu de préférence à partir de l'hydrogénation d'acide acétique par un procédé à faible énergie. Le produit éthanolique brut est séparé dans une colonne pour produire un courant de distillat renfermant de l'acétate d'éthyle et un courant de résidu renfermant de l'éthanol, de l'acide acétique et de l'eau. Le produit éthanolique est récupéré dans une seconde colonne sous la forme d'un courant latéral d'éthanol.
PCT/US2011/046503 2011-08-03 2011-08-03 Procédé de récupération d'éthanol dans une colonne de distillation à évacuation latérale Ceased WO2013019236A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2013074570A1 (fr) * 2011-11-18 2013-05-23 Celanese International Corporation Procédé pour la récupération d'éthanol à partir d'un procédé d'hydrogénolyse

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013074570A1 (fr) * 2011-11-18 2013-05-23 Celanese International Corporation Procédé pour la récupération d'éthanol à partir d'un procédé d'hydrogénolyse
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process

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