WO2011097220A2 - Procédé de production d'éthanol à l'aide d'une colonne de distillation extractive - Google Patents
Procédé de production d'éthanol à l'aide d'une colonne de distillation extractive Download PDFInfo
- Publication number
- WO2011097220A2 WO2011097220A2 PCT/US2011/023328 US2011023328W WO2011097220A2 WO 2011097220 A2 WO2011097220 A2 WO 2011097220A2 US 2011023328 W US2011023328 W US 2011023328W WO 2011097220 A2 WO2011097220 A2 WO 2011097220A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethanol
- column
- residue
- distillate
- water
- Prior art date
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 570
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000000895 extractive distillation Methods 0.000 title claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 306
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910001868 water Inorganic materials 0.000 claims abstract description 86
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 221
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
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- 239000007788 liquid Substances 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
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- 229910017052 cobalt Inorganic materials 0.000 claims description 14
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- HYERJXDYFLQTGF-UHFFFAOYSA-N rhenium Chemical compound [Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re] HYERJXDYFLQTGF-UHFFFAOYSA-N 0.000 claims 3
- 238000000926 separation method Methods 0.000 abstract description 18
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—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
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
Definitions
- the present invention relates generally to processes for producing ethanol and, in particular, to processes for producing ethanol from the hydrogenation of acetic acid.
- 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 for fuels or 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.
- the present invention is directed to a process for purifying a crude ethanol product, the process comprising hydrogenating an acetic acid feed, stream in a reactor in the presence of a catalyst to form a crude ethanol product; separating at least a portion of the crude ethanol product in a first column into a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid; separating at least a portion of the first distillate in a second column into a second distillate comprising ethyl acetate and a second residue comprising ethanol and water, wherein the second column is an extractive distillation column; feeding an extraction agent to the second column; and separating at least a portion of the second residue in a third column into a third distillate comprising ethanol and a third residue comprising water.
- the present invention is directed to a process for purifying a crude ethanol product, the process comprising hydrogenating an acetic acid feed stream in a reactor in the presence of a catalyst to form a crude ethanol product; separating at least a portion of the crude ethanol product in a first column into a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid; separating at least a portion of the first distillate in a second column into a second distillate comprising ethyl acetate and a second residue comprising ethanol and water; and separating at least a portion of the second residue in a third column into a third distillate comprising ethanol and a third residue comprising water; wherein at least a portion of the third residue is directly or indirectly returned to the second column.
- the present invention is directed to a process for purifying a crude ethanol product comprising ethanol, water, acetic acid, acetaldehyde and ethyl acetate, the process comprising separating the crude ethanol product in a first column into a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid; separating the first distillate in a second column into a second distillate comprising ethyl acetate and a second residue comprising ethanol and water; separating the second residue in a third column into a third distillate comprising ethanol and a third residue comprising water; and
- FIG. 1 is a schematic diagram of a hydrogenation system in accordance with one embodiment of the present invention.
- FIG. 2 is a schematic diagram of a hydrogenation system in accordance with another embodiment of the present invention.
- FIG. 3 is a graph of the ethanol and ethyl acetate concentration changes in the second distillate with the addition of an extraction agent to the second column.
- the present invention relates to processes for recovering ethanol from a crude ethanol product.
- the present invention relates to processes for recovering and/or purifying ethanol from a crude ethanol product, which preferably is formed in a process for hydrogenating acetic acid in the presence of a catalyst.
- the process optionally employs an extractive distillation column to facilitate separation of these components.
- ethanol advantageously may be separated from the crude ethanol product even when the content of ethyl acetate and/or water in the crude ethanol product is sufficient to form such azeotropes.
- the extraction agent employed in the extractive distillation column may comprise water obtained from an external source, from a portion of a recycled stream within the process, or combinations thereof.
- the extraction agent employed in the extractive distillation column preferably comprises a recycled stream from a column that separates ethanol from water.
- the extraction agent comprises at least a portion of the residue from this column, which preferably comprises water.
- Embodiments of the present invention beneficially may be used in applications for recovery and/or purifying of ethanol on an industrial scale.
- the recycled stream comprising the extraction agent further promotes the separation in the extractive distillation column.
- the recycled stream may also promote the separation of ethanol from the crude ethanol product.
- the process of the present invention may improve efficiency and reduce cost by decrease water use and consumption. In addition, such embodiments may advantageously reduce waste generation.
- the process of the present invention may use the recycle water to integrate the heat throughout the system and reduce energy consumption.
- the process further includes a step of separating acetaldehyde from the crude ethanol product and returning separated acetaldehyde to the reaction process, preferably to the acetic acid feed, to the vaporizer, or to the hydrogenation reactor.
- the returned acetaldehyde may be reacted under the hydrogenation conditions.
- the acetaldehyde is separated from a stream comprising ethyl acetate derived from the crude ethanol product. This may allow a major portion of the ethyl acetate to be removed from the process without building up ethyl acetate throughout the separation process.
- Suitable hydrogenation catalysts include catalysts comprising a first metal and optionally one or more of a second metal, a third metal or 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, VHI transitional metals, a lanthanide metal, an actinide metal or a metal selected from any of Groups III A, 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/ruthenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium, and ruthenium/iron.
- Exemplary catalysts are further described in U.S. Patent Nos. 7,608,744, and 7,863,489, and U.S. Publication No. 2010/0197485, the entireties of which are 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 demand for platinum.
- the catalyst optionally 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 catalyst includes two or more metals, e.g., a first metal and a second metal
- the first metal optionally 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 and 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, ruthenium, copper, zinc, platinum, tin, and rhenium. More preferably, the third metal is selected from cobalt, palladium, and ruthenium.
- the total weight of the third metal preferably is from 0.05 and 4 wt.%, e.g., from 0.1 to 3 wt.%, or from 0.1 to 2 wt.%.
- the exemplary catalysts further comprise a support or a modified support, meaning 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 wt.% to 99.9 wt.%, e.g., from 78 wt.% to 97 wt.%, or from 80 wt.% to 95 wt.%.
- the support modifier is present in an amount from 0.1 wt.% to 50 wt.%, e.g., from 0.2 wt.% to 25 wt.%, from 0.5 wt.% to 15 wt.%, or from 1 wt.% to 8 wt.%, based on the total weight of the catalyst.
- 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 II A 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 is 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 metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.
- the support modifier is selected from the group consisting of oxides and metasilicates of any of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, as well as mixtures of any of the foregoing.
- the support modifier is a calcium silicate, and more preferably calcium metasilicate (CaSi0 3 ). If the 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 SS61138 High Surface Area (HSA) Silica Catalyst Carrier from Saint Gobain NorPro.
- the Saint-Gobain NorPro SS61138 silica contains approximately 95 wt.% high surface area silica; a surface area of about 250 m /g; a median pore diameter of about 12 nm; an average pore volume of about 1.0 cm 3 /g as measured by mercury intrusion porosimetry and a packing density of about 0.352 g/cm 3 (22 lb/ft 3 ).
- a preferred silica/alumina support material is KA-160 (Sud Chemie) silica spheres having a nominal diameter of about 5 mm, a density of about 0.562 g/ml, in absorptivity of about
- 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.
- the metals of the catalysts may be dispersed throughout the support, coated on the outer surface of the support (egg shell) or decorated on the surface of the support.
- 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. Patent Nos. 7,608,744, and 7,863,489, and U.S. Publication No. 2010/0197485, the entireties of which are incorporated herein by reference.
- 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, as one of skill in the art will readily appreciate.
- 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.
- radial flow reactor or reactors may be employed, or a series of reactors may be employed with or with out 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 BCPa (about 1.5 to 435 psi), 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 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.
- synthesis gas syn gas
- Methanol carbonylation processes suitable for production of acetic acid are described in U.S. Patent Nos. 7,208,624, 7,115,772, 7,005,541, 6,657,078, 6,627,770, 6,143,930, 5,599,976, 5,144,068, 5,026,908, 5,001,259, and 4,994,608, the disclosure of which is incorporated herein by reference.
- the production of ethanol may be integrated with such methanol carbonylation processes.
- U.S. Patent No. RE 35,377 also incorporated herein by reference, provides a method for the production of methanol by conversion of 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. These other compounds may also be hydrogenated in the processes of the present invention.
- carboxylic acids such as propanoic acid or its anhydride, may be beneficial in producing propanol.
- acetic acid in vapor form may be taken directly as crude product from the flash vessel of a methanol carbonylation unit of the class described in U.S. Patent No. 6,657,078, the entirety of which is incorporated herein by reference.
- the crude vapor product for example, 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 can 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 transferred to the vapor state by passing hydrogen, recycle gas, another suitable gas, or mixtures thereof through the acetic acid at a temperature below the boiling point of acetic acid, thereby humidifying the carrier gas with acetic acid vapors, followed by heating the mixed vapors up to the reactor inlet temperature.
- the acetic acid is transferred to the vapor 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 reactor inlet temperature.
- 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%. Although 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.
- 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 50 mole % of the converted acetic acid is converted to ethanol, we refer to the ethanol selectivity as 50%.
- 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 not detectable.
- 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 crude ethanol product produced by the hydrogenation process, before any subsequent processing, such as purification and separation will typically comprise unreacted acetic acid, ethanol and water.
- the term "crude ethanol product” refers to any composition comprising from 5 to 70 wt.% ethanol and from 5 to 35 wt.% water.
- the crude ethanol product comprises ethanol in an amount from 5 wt.% to 70 wt.%, e.g., from 10 wt.% to 60 wt.%, or from 15 wt.% to 50 wt.%, based on the total weight of the crude ethanol product.
- the crude ethanol product contains at least 10 wt.% ethanol, at least 15 wt.% ethanol or at least 20 wt.% ethanol.
- the crude ethanol product typically will further comprise unreacted acetic acid, depending on conversion, for example, in an amount of less than 90 wt.%, e.g., less than 80 wt.% or less than 70 wt.%.
- the unreacted acetic acid is preferably from 0 to 90 wt.%, e.g., from 5 to 80 wt.%, from 15 to 70 wt.%, from 20 to 70 wt.% or from 25 to 65 wt.%.
- water will generally be present in the crude ethanol product, for example, in amounts ranging from 5 to 35 wt.%, e.g., from 10 to 30 wt.% or from 10 to 26 wt.%.
- Ethyl acetate may also be produced during the hydrogenation of acetic acid or through side reactions and may be present, for example, in amounts ranging from 0 to 20 wt.%, e.g., from 0 to 15 wt.%, from 1 to 12 wt.% or from 3 to 10 wt.%.
- Acetaldehyde may also be produced through side reactions and may be present, for example, in amounts ranging from 0 to 10 wt.%, e.g., from 0 to 3 wt.%, from 0.1 to 3 wt.% or from 0.2 to 2 wt.%.
- Other components such as, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide, if detectable, collectively may be present in amounts less than 10 wt.%, e.g., less than 6 wt .% or less than 4 wt.%.
- Acetic Acid 0 to 90 5 to 80 15 to 70 20 to 70
- FIG. 1 shows a hydrogenation system 100 suitable for the hydrogenation of acetic acid and separating ethanol from the crude reaction mixture according to one embodiment of the invention.
- System 100 comprises reaction zone 101 and distillation zone 102.
- Reaction zone 101 comprises reactor 103, hydrogen feed line 104 and acetic acid feed line 105.
- Distillation zone 102 comprises flasher 106, first column 107, second column 108, and third column 109.
- a portion or all of third residue in line 121 from the third column 109 preferably is recycled to the second column 108.
- FIG. 1 illustrates the third residue being directly recycled to the second column, in other embodiments the third residue may be stored in a holding tank and indirectly recycled to the second column.
- only a portion, e.g., an aliquot portion, of the third residue is recycled, directly or indirectly, to the second column. It is also possible to utilize water from another source via line 127 to replace a portion or all of the third residue that may be fed to the second column as the extraction agent.
- Hydrogen and acetic acid are fed to a vaporizer 110 via lines 104 and 105, respectively, to create a vapor feed stream in line 111 that is directed to reactor 103.
- lines 104 and 105 may be combined and jointly fed to the vaporizer 110, e.g., in one stream containing both hydrogen and acetic acid.
- the temperature of the vapor feed stream in line 111 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 110, as shown in FIG. 1, and may be recycled thereto.
- FIG. 1 shows line 111 being directed to the top of reactor 103, line 111 may be directed to the side, upper portion, or bottom of reactor 103. Further modifications and additional components to reaction zone 101 are described below.
- Reactor 103 contains the catalyst that is used in the hydrogenation of the carboxylic acid, preferably acetic acid.
- one or more guard beds may be used 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 are known in the art and include, for example, carbon, silica, alumina, ceramic, or resins.
- the guard bed media is functionalized to trap particular species such as sulfur or halogens.
- a crude ethanol product stream is withdrawn, preferably continuously, from reactor 103 via line 112.
- the crude ethanol product stream may be condensed and fed to flasher 106, which, in turn, provides a vapor stream and a liquid stream.
- the flasher 106 in one embodiment preferably operates at a temperature of from 50°C to 500°C, e.g., from 70°C to 400°C or from 100°C to 350°C.
- the pressure of flasher 106 preferably is from 50 KPa to 2000 KPa, e.g., from 75 KPa to 1500 KPa or from 100 to 1000 KPa.
- the temperature and pressure of the flasher is similar to the temperature and pressure of the reactor 103.
- the vapor stream exiting the flasher may comprise hydrogen and hydrocarbons, which may be purged and/or returned to reaction zone 101 via line 113. As shown in FIG. 1, the returned portion of the vapor stream passes through compressor 114 and is combined with the hydrogen feed and co-fed to vaporizer 110.
- the liquid from flasher 106 is withdrawn and pumped via line 115 to the side of first column 107, also referred to as the acid separation column.
- the contents of line 115 may be substantially similar to the crude ethanol product obtained from the reactor, except that the composition has substantially no hydrogen, carbon dioxide, methane or ethane, which are removed by the flasher 106.
- Exemplary components of liquid in line 115 are provided in Table 2. It should be understood that liquid line 115 may contain other components, not listed, such as components in the feed.
- 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
- the feed composition e.g., line 115
- the feed composition 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.
- the acid separation column 107 may be skipped and line 115 may be introduced directly to second column 108, also referred to herein as a light ends column.
- line 115 is introduced in the lower part of first column 107, e.g., lower half or lower third. In first column 107, unreacted acetic acid, a portion of the water, and other heavy components, if present, are removed from the composition in line
- 116 to the vaporizer 110 may reduce the amount of heavies that need to be purged from vaporizer 110. Reducing the amount of heavies to be purged may improve efficiencies of the process while reducing byproducts.
- First column 107 also forms an overhead distillate, which is withdrawn in line 117, and which may be condensed and refluxed, for example, at a ratio of from 10:1 to 1 :10, e.g., from 3:1 to 1 :3 or from 1:2 to 2:1.
- any of columns 107, 108 , 109, or 123 in FIG. 2 may comprise any distillation column capable of separation and/or purification.
- the columns preferably comprise tray columns 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.
- structured 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 FIGS. 1 and 2.
- 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 in some embodiments.
- the heat that is provided to 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.
- FIGS. 1 and 2 additional reactors, flashers,.
- condensers heating elements, and other components may be used in embodiments of the present invention.
- various condensers, pumps, compressors, reboilers, drums, valves, connectors, separation vessels, etc. normally employed in carrying out chemical processes may also be combined and employed in the processes of the present invention.
- temperatures and pressures employed in any of 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 may be employed as well as superatmospheric pressures. 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. It will be recognized by those skilled in the art that 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 temperature of the residue exiting in line 116 from column 107 preferably is from 95°C to 120°C, e.g., from 110°C to 117°C or from 111°C to 115°C.
- the temperature of the distillate exiting in line 117 from column 107 preferably is from 70°C to 110°C, e.g., from 75°C to 95°C or from 80°C to 90°C.
- Column 107 preferably operates at ambient pressure. In other embodiments, 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.
- 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, such as components in the feed.
- the distillate and residue of the first column may also be referred to as the "first distillate” or “first residue.”
- the distillates or residues of the other columns may also be referred to with similar numeric modifiers (second, third, etc.) in order to distinguish them from one another, but such modifiers should not be construed as requiring any particular separation order.
- the crude ethanol product exiting reactor 103 in line 112 may comprise ethanol, acetic acid (unconverted), ethyl acetate, and water.
- a non-catalyzed equilibrium reaction may occur between the components contained in the crude ethanol product until it is added to flasher 106 and/or first column 107. This equilibrium reaction tends to drive the crude ethanol product to an equilibrium between ethanol/acetic acid and ethyl acetate/water, as shown below.
- a holding tank (not shown), is included between the reaction zone 101 and distillation zone 102 for temporarily storing the liquid component from line 115 for up to 5 days, e.g., up to 1 day, or up to 1 hour.
- no tank is included and the condensed liquids are fed directly to the first distillation column 107.
- the rate at which the non-catalyzed reaction occurs may increase as the temperature of the crude ethanol product, e.g., in line 115, increases. These reaction rates may be particularly problematic at temperatures exceeding 30°C, e.g., exceeding 40°C or exceeding 50°C.
- the temperature of liquid components in line 115 or in the optional holding tank is maintained at a temperature less than 40°C, e.g., less than 30°C or less than 20°C.
- One or more cooling devices may be used to reduce the temperature of the liquid in line 115.
- a holding tank (not shown) may be included between the reaction zone 101 and distillation zone 102 for temporarily storing the liquid component from line 115, for example from 1 to 24 hours, optionally at a temperature of about 21°C, and corresponding to an ethyl acetate formation of from 0.01 wt.% to 1.0 wt.% respectively.
- the rate at which the non-catalyzed reaction occurs may increase as the temperature of the crude ethanol product is increased.
- the temperature of liquid components in line 115 or in the optional holding tank is maintained at a temperature less than 21°C, e.g., less than 4°C or less than -10°C.
- the distillate, e.g., overhead stream, of column 107 optionally is condensed and refluxed as shown in FIG. 1 , preferably, at a reflux ratio of 1 : 5 to 10:1.
- the distillate in line 117 preferably comprises ethanol, ethyl acetate, and water, along with other impurities, which may be difficult to separate due to the formation of binary and tertiary azeotropes.
- the first distillate in line 117 is introduced to the second column 108, also referred to as the "light ends column,” preferably in the middle part of column 108, e.g., middle half or middle third.
- the second column 108 is an extractive distillation column, and an extraction agent is added thereto via lines 121 and/or 127.
- Extractive distillation is a method of separating close boiling components, such as azeotropes, by distilling the feed in the presence of an extraction agent.
- the extraction agent preferably has a boiling point that is higher than the compounds being separated in the feed.
- the extraction agent is comprised primarily of water.
- the first distillate in line 117 that is fed to the second column 108 comprises ethyl acetate, ethanol, and water. These compounds tend to form binary and ternary azeotropes, which decrease separation efficiency.
- the extraction agent comprises the third residue in line 121.
- the recycled third residue in line 121 is fed to second column 108 at a point higher than the first distillate in line 117.
- the recycled third residue in line 121 is fed near the top of second column 108 or fed, for example, above the feed in line 117 and below the reflux line from the condensed overheads.
- the third residue in line 121 is continuously added near the top of the second column 108 so that an appreciable amount of the third residue is present in the liquid phase on all of the trays below.
- the extraction agent is fed from a source outside of the process 100 via line 127 to second column 108.
- this extraction agent comprises water.
- the molar ratio of the water in the extraction agent to the ethanol in the. feed to the second column is preferably at least 0.5: 1 , e.g., at least 1:1 or at least 3:1.
- preferred molar ratios may range from 0.5:1 to 8:1, e.g., from 1 :1 to 7:1 or from 2:1 to 6.5:1.
- Higher molar ratios may be used but with diminishing returns in terms of the additional ethyl acetate in the second distillate and decreased ethanol concentrations in the second column distillate, as shown in FIG. 3.
- an additional extraction agent such as water from an external source, dimethylsulfoxide, glycerine, diethylene glycol, 1-naphthol, hydroquinone, ⁇ , ⁇ '- dimethylformamide, 1 ,4-butanediol; ethylene glycol- 1, 5 -pentanediol; propylene glycol- tetraethylene glycol-poly ethylene glycol; glycerine-propylene glycol-tetraethylene glycol- 1,4- butanediol, ethyl ether, methyl formate, cyclohexane, N,N'-dimethyl-l,3-propanediamine, ⁇ , ⁇ '- dimethylethylenediamine, diethylene triamine, hexamethylene diamine and 1,3-diaminopentane, an alkylated thiopene, dodecane, tridecane, tetradecane and chlorinated paraffins
- the additional extraction agent may be combined with the recycled third residue in line 121 and co-fed to the second column 108.
- the additional extraction agent may also be added separately to the second column.
- the extraction agent comprises an extraction agent, e.g., water, derived from an external source via line 127 and none of the extraction agent is derived from the third residue.
- Second column 108 may be a tray or packed column.
- second column 108 is a tray column having from 5 to 70 trays, e.g., from 15 to 50 trays or from 20 to 45 trays.
- second column 108 may vary, when at atmospheric pressure the temperature of the second residue exiting in line 118 from second column 108 preferably is from 60°C to 90°C, e.g., from 70°C to 90°C or from 80°C to 90°C.
- the temperature of the second distillate exiting in line 120 from second column 108 preferably is from 50°C to 90°C, e.g., from 60°C to 80°C or from 60°C to 70°C.
- Column 108 may operate at atmospheric pressure.
- the pressure of second column 108 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 108 are provided in Table 4 below. It should be understood that the distillate and residue may also contain other components, not listed, such as components in the feed.
- the recycling of the third residue promotes the separation of ethyl acetate from the residue of the second column 108.
- the weight ratio of ethyl acetate in the second residue to second distillate preferably is less than 0.4: 1, e.g., less than 0.2: 1 or less than 0.1 : 1.
- the weight ratio of ethyl acetate in the second residue to ethyl acetate in the second distillate approaches zero.
- the weight ratio of ethanol in the second residue to second distillate preferably is at least 3:1, e.g., at least 6: 1 , at least 8: 1 , at least 10:1 or at least 15:1. All or a portion of the third residue is recycled to the second column. In one embodiment, all of the third residue may be recycled until process 100 reaches a steady state and then a portion of the third residue is recycled with the remaining being purged from the system 100. The composition of the second residue will tend to have lower amounts of ethanol than when the third residue is not recycled.
- the composition of the second residue comprises less than 30 wt.% ethanol, e.g., less than 20 wt.% or less than 15 wt.%.
- the majority of the second residue preferably comprises water.
- the extractive distillation step advantageously also reduces the amount of ethyl acetate that is sent to the third column, which is highly beneficial in ultimately forming a highly pure ethanol product.
- the second residue from the bottom of second column 108 which comprises ethanol and water, is fed via line 118 to third column 109, also referred to as the "product column.” More preferably, the second residue in line 118 is introduced in the lower part of third column 109, e.g., lower half or lower third.
- Third column 109 recovers ethanol, which preferably is substantially pure with respect to organic impurities and other than the azeotropic water content, as the distillate in line 119.
- the distillate of third column 109 preferably is refluxed as shown in FIG. 1 , for example, at a reflux ratio of from 1 : 10 to 10: 1, e.g., from 1 :3 to 3:1 or from 1 :2 to 2:1.
- the third residue in line 121 which preferably comprises primarily water, preferably is returned to the second column 108 as an extraction agent as shown in FIG. 1 , and as described above.
- a first portion of the third residue in line 121 is recycled to the second column and a second portion is purged and removed from the system.
- the second portion of water to be purged is substantially similar to the amount water formed in the hydrogenation of acetic acid.
- a portion of the third residue may be used to hydrolyze any other stream, such as one or more streams comprising ethyl acetate.
- third residue may also be returned indirectly, for example, by storing a portion or all of the third residue in a tank (not shown) or treating the third residue to further separate any minor components such as aldehydes, higher molecular weight alcohols, or esters in one or more additional columns (not shown).
- Third column 109 is preferably a tray column as described above and operates at atmospheric pressure or optionally at pressures above or below atmospheric pressure.
- the temperature of the third distillate exiting in line 119 from third column 109 preferably is from 60°C to 110°C, e.g., from 70°C to 100°C or from 75°C to 95°C.
- the temperature of the third residue exiting from third column 109 preferably is from 70°C to 115°C, e.g., from 80°C to I 10°C or from 85°C to 105°C.
- Exemplary components of the distillate and residue compositions for third column 109 are provided in Table 5 below. It should be understood that the distillate and residue may also contain other components, not listed, such as components in the feed.
- the third residue in line 121 is withdrawn from third column 109 at a temperature higher than the operating temperature of the second column 108.
- the third residue in line 121 is integrated to heat one or more other streams or is reboiled prior to be returned to the second column 108.
- Any of the compounds that are carried through the distillation process from the feed or crude reaction product generally remain in the third distillate in amounts of less 0.1 wt.%, based on the total weight of the third distillate composition, e.g., less than 0.05 wt.% or less than 0.02 wt.%.
- one or more side streams may remove impurities from any of the columns 107, 108 and/or 109 in the system 100.
- at least one side stream is used to remove impurities from the third column 109. The impurities may be purged and/or retained within the system 100.
- the third distillate in line 119 may be further purified to form an anhydrous ethanol product stream, i.e., "finished anhydrous ethanol," using one or more additional separation systems, such as, for example, distillation columns (e.g., a finishing column) or molecular sieves.
- additional separation systems such as, for example, distillation columns (e.g., a finishing column) or molecular sieves.
- the second distillate preferably is refluxed as shown in FIG. 1, optionally at a reflux ratio of 1 :10 to 10:1, e.g., from 1 :5 to 5:1 or from 1:3 to 3:1.
- the second distillate may be purged or recycled to the reaction zone.
- the second distillate in line 120 is further processed in a fourth column 123 as shown in FIG. 2.
- the second distillate in line 120 primarily comprises ethyl acetate, the ethyl acetate is not substantially pure and contains additional components. These additional components may be processed and removed from the second distillate.
- the system 100 in FIG. 2 is similar to FIG. 1, with the addition that the second distillate in line 120 is fed to fourth column 123, also referred to as the "acetaldehyde removal column.”
- fourth column 123 the second distillate is separated into a fourth distillate, which comprises acetaldehyde, in line 124.
- fourth column 123 the second distillate is separated into a fourth distillate, which comprises acetaldehyde, in line 124 and a fourth residue, which comprises ethyl acetate, in line 125.
- the fourth distillate preferably is refluxed at a reflux ratio of from 1 :20 to 20:1, e.g., from 1 :15 to 15:1 or from 1 :10 to 10:1, and a portion of the fourth distillate is returned to the reaction zone 101 as shown by line 124.
- the fourth distillate may be combined with the acetic acid feed, added to the vaporizer 110, or added directly to the reactor 103. As shown, the fourth distillate is co-fed with the acetic acid in feed line 105 to vaporizer 110.
- acetaldehyde may be hydrogenated to form ethanol
- the recycling of a stream that contains acetaldehyde to the reaction zone increases the yield of ethanol and decreases byproduct and waste generation.
- the acetaldehyde may be collected and utilized, with or without further purification, to make useful products including but not limited to n-butanol, 1,3-butanediol, and/or
- the fourth residue of fourth column 123 may be purged via line 125.
- the fourth residue primarily comprises ethyl acetate and ethanol, which may be suitable for use as a solvent mixture or in the production of esters.
- the acetaldehyde is removed from the second distillate in fourth column 123 such that no detectable amount of acetaldehyde is present in the residue of column 123.
- Fourth column 123 is preferably a tray column as described above and preferably operates above atmospheric pressure.
- the pressure is from 120 KPa to 5,000 KPa, e.g., from 200 KPa to 4,500 KPa, or from 400 KPa to 3,000 KPa.
- the fourth column 123 may operate at a pressure that is higher than the pressure of the other columns.
- the temperature of the fourth distillate exiting in line 124 from fourth column 123 preferably is from 60°C to 110°C, e.g., from 70°C to 100°C or from 75°C to 95°C.
- the temperature of the residue exiting from fourth column 125 preferably is from 70°C to 115°C, e.g., from 80°C to 110°C or from 85°C to 110°C.
- Exemplary components of the distillate and residue compositions for fourth column 123 are provided in Table 6 below. It should be understood that the distillate and residue may also contain other components, not listed, such as components in the feed.
- FIG. 2 also shows that the third residue in line 121 is recycled to second column 108.
- recycling the third residue further reduces the aldehyde components in the second residue and concentrates these aldehyde components in the distillate stream 120 and thereby sent to the fourth column 123, wherein the aldehydes may be more easily separated in the fourth column 123.
- Such embodiments also provide a finished ethanol product that preferably has low amounts of aldehydes and esters.
- the finished ethanol composition obtained by the processes of the present invention preferably comprises 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 finished ethanol composition.
- Exemplary finished ethanol compositional ranges are provided below in Table 7.
- 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 2 o alcohols.
- the amount of isopropanol in the finished ethanol is from 80 to 1,000 wppm, e.g., from 95 to 1,000 wppm, from 100 to 700 wppm, or from 150 to 500 wppm.
- the finished ethanol composition preferably is substantially free of acetaldehyde and may comprise less than 8 wppm of acetaldehyde, e.g., less than 5 wppm or less than 1 wppm.
- the finished ethanol composition produced by the embodiments of the present invention may be used in a variety of applications including fuels, solvents, chemical feedstocks, pharmaceutical products, cleansers, sanitizers, hydrogenation transport or consumption.
- the finished ethanol composition may be blended with gasoline for motor vehicles such as automobiles, boats and small piston engine aircrafts.
- 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, photochemicals and latex processing.
- the finished ethanol composition may also be used a chemical feedstock to make other chemicals such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers, ethylamines, aldehydes, and higher alcohols, especially butanol.
- the finished ethanol composition may be esterified with acetic acid or reacted with polyvinyl acetate.
- the finished ethanol composition may be dehydrated to produce ethylene. Any of known dehydration catalysts can be employed in to dehydrate ethanol, such as those described in U.S. Pub. Nos.
- a zeolite catalyst for example, may be employed as the dehydration catalyst.
- the zeolite has a pore diameter of at least about 0.6 nm, and 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.
- a crude ethanol product comprising ethanol, acetic acid, water and ethyl acetate was produced by reacting a vaporized feed comprising 95.2 wt.% acetic acid and 4.6, wt.% water with hydrogen in the presence of a catalyst comprising 1.6 wt.% platinum and 1 wt.% tin supported on 1/8 inch calcium silicate modified silica extrudates at an average temperature of 291 °C, an outlet pressure of 2,063 KPa. Unreacted hydrogen was recycled back to the inlet of the reactor such that the total H 2 /acetic acid molar ratio was 5.8 at a GHSV of 3,893 hr "1 .
- the crude ethanol product was fed to the first column at a feed rate of 20 g/min.
- the composition of the liquid feed is provided in Table 8.
- the first column is a 2 inch diameter Oldershaw with 50 trays.
- the column was operated at a temperature of 115°C at atmospheric pressure. Unless otherwise indicated, a column operating temperature is the temperature of the liquid in the reboiler and the pressure at the top of the column is atmospheric (approximately one atmosphere).
- the column differential pressure between the trays in the first column was 7.4 KPa.
- the first residue was withdrawn at a flow rate of 12.4 g/min and returned to the hydrogenation reactor.
- the first distillate was condensed and refiuxed at a 1 : 1 ratio at the top of the first column, and a portion of the distillate was introduced to the second column at a feed rate of 7.6 g/min.
- the second column is a 2 inch diameter Oldershaw design equipped with 25 trays.
- the second column was operated at a temperature of 82°C at atmospheric pressure.
- the column differential pressure between the trays in the second column was 2.6 KPa.
- the second residue was withdrawn at a flow rate of 5.8 g/min and directed to the third column.
- the second distillate was refiuxed at a ratio of 4.5:0.5 and the remaining distillate was collected for analysis. No extraction agent was fed to the second column in this example.
- Table 8 The compositions of the feed, distillates, and residues are provided in Table 8.
- Example 1 The crude ethanol product of Example 1 was processed under similar conditions, except that an extraction agent, deionized water, was fed to the second column.
- the molar ratio of the water in the extraction agent to the ethanol in the feed to the second column was 6.4:1.
- the use of an extraction agent in the second column provided for increased amounts of ethyl acetate in the distillate and decreased amounts of ethanol in the distillate as shown in Table 9.
- the change in the weight percent from Table 8 to Table 9 ("Distillate ⁇ %") with the extraction agent is also provided in Table 9.
- a crude ethanol product comprising ethanol, acetic acid, water and ethyl acetate was produced by reacting a vaporized feed comprising 96.3 wt.% acetic acid and 4.3 wt.% water with hydrogen in the presence of a catalyst comprising 1.6 wt.% platinum and 1% tin supported on 1/8 inch calcium silicate modified silica extrudates at an average temperature of 290°C, an outlet pressure of 2,049 KPa. Unreacted hydrogen was recycled back to the inlet of the reactor such that the total H 2 /acetic acid molar ratio was 10.2 at a GHSV of 1,997 hr "1 .
- the crude ethanol product was fed to the first column at a feed rate of 20 g/min.
- the composition of the liquid feed is provided in Table 10.
- the first column is a 2 inch diameter Oldershaw with 50 trays.
- the column was operated at a temperature of 116 °C at atmospheric pressure.
- the column differential pressure between the trays in the first column was 8.1 KPa.
- the first residue was withdrawn at a flow rate of 10.7 g/min and returned to the hydrogenation reactor.
- the first distillate was condensed and refluxed at a 1 : 1 ratio at the top of the first column, and a portion of the distillate was introduced to the second column at a feed rate of 9.2 g/min.
- the second column is a 2 inch diameter Oldershaw design equipped with 25 trays.
- the second column was operated at a temperature of 82°C at atmospheric pressure.
- the column differential pressure between the trays in the second column was 2.4 KPa.
- the second residue was withdrawn at a flow rate of 7.1 g/min and directed to the third column.
- the second distillate was refluxed at a ratio of 4.5:0.5 and the remaining distillate was collected for analysis. No extraction agent was fed to the second column in this example.
- Table 10 The compositions of the feed, distillates, and residues are provided in Table 10.
- Example 2 The crude ethanol product of Example 2 was processed under similar conditions, except that an extraction agent, deionized water, was fed to the second column.
- the molar ratio of the water in the extraction agent to the ethanol in the feed to the second column was 4:1.
- the use of an extraction agent in the second column provided for increased amounts of ethyl acetate in the distillate and decreased amounts of ethanol in the distillate as shown in Table 11.
- the change in the weight percent from Table 10 to Table 11 ("Distillate ⁇ %") with the extraction agent is also provided in Table 11.
- FIG. 3 is a graph of the ethanol and ethyl acetate concentration changes in the second distillate achieved by varying the mole ratio of water in the extraction agent to ethanol in feed directed to the second column.
- the concentrations of ethanol and ethyl acetate are normalized in FIG. 3 to a common "water-free" basis for comparison purposes.
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Abstract
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2012137190/04A RU2012137190A (ru) | 2010-02-02 | 2011-02-01 | Способ получения этанола при использовании колонны экстракционной дистилляции |
SG2012055281A SG182735A1 (en) | 2010-02-02 | 2011-02-01 | Process for producing ethanol using an extractive distillation column |
JP2012551384A JP2013518820A (ja) | 2010-02-02 | 2011-02-01 | 抽出蒸留カラムを用いるエタノールの製造方法 |
MX2012008937A MX2012008937A (es) | 2010-02-02 | 2011-02-01 | Proceso para producir etanol utilizando una columna de destilacion por extraccion. |
CN201180001870.5A CN102414153B (zh) | 2010-02-02 | 2011-02-01 | 使用提取蒸馏塔生产乙醇的方法 |
EP11702775.5A EP2531470B1 (fr) | 2010-02-02 | 2011-02-01 | Procédé de production d'éthanol à l'aide d'une colonne de distillation extractive |
CA2787444A CA2787444A1 (fr) | 2010-02-02 | 2011-02-01 | Procede de production d'ethanol a l'aide d'une colonne de distillation extractive |
AU2011213059A AU2011213059A1 (en) | 2010-02-02 | 2011-02-01 | Process for producing ethanol using an extractive distillation column |
BR112012019270A BR112012019270A2 (pt) | 2010-02-02 | 2011-02-01 | processo para a produção de etanol usando uma coluna de destilação extrativa |
IL221222A IL221222A0 (en) | 2010-02-02 | 2012-07-31 | Process for producing ethanol using an extractive distillation column |
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US12/852,305 | 2010-08-06 | ||
US12/852,305 US8304587B2 (en) | 2010-05-07 | 2010-08-06 | Process for producing ethanol using an extractive distillation column |
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US8927787B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process for controlling a reboiler during alcohol recovery and reduced ester formation |
US8927784B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process to recover alcohol from an ethyl acetate residue stream |
CN103080054A (zh) * | 2011-04-26 | 2013-05-01 | 国际人造丝公司 | 使用分别具有不同催化剂的多个床生产乙醇的方法 |
WO2012149148A1 (fr) * | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Distillation extractive d'éthanol brut |
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US9000235B2 (en) | 2011-06-16 | 2015-04-07 | Celanese International Corporation | Extractive distillation of crude alcohol product |
WO2012173647A1 (fr) * | 2011-06-16 | 2012-12-20 | Celanese International Corporation | Distillation extractive d'un produit alcoolisé brut |
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JPWO2013035849A1 (ja) * | 2011-09-09 | 2015-03-23 | 宝酒造株式会社 | 無水アルコールの製造方法、並びに、無水アルコール |
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