WO2013070213A1 - Iintegrated process for producing ethanol from methanol with water balance control - Google Patents

Iintegrated process for producing ethanol from methanol with water balance control Download PDF

Info

Publication number
WO2013070213A1
WO2013070213A1 PCT/US2011/060012 US2011060012W WO2013070213A1 WO 2013070213 A1 WO2013070213 A1 WO 2013070213A1 US 2011060012 W US2011060012 W US 2011060012W WO 2013070213 A1 WO2013070213 A1 WO 2013070213A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
acetic acid
ethanol
stream
column
Prior art date
Application number
PCT/US2011/060012
Other languages
French (fr)
Inventor
Victor J. Johnston
Mark Scates
Ronald David Shaver
Raymond Zinobile
Original Assignee
Celanese International Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Celanese International Corporation filed Critical Celanese International Corporation
Priority to PCT/US2011/060012 priority Critical patent/WO2013070213A1/en
Publication of WO2013070213A1 publication Critical patent/WO2013070213A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/147Preparation 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
    • C07C29/149Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12Preparation 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10General improvement of production processes causing greenhouse gases [GHG] emissions
    • Y02P20/12Energy input
    • Y02P20/121Energy efficiency measures, e.g. energy management
    • Y02P20/125Process integration
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/582Recycling of unreacted starting or intermediate materials

Abstract

Described is an integrated process for producing ethanol from acetic acid in which the water from ethanol production is used to control water balance in the acetic acid production. In one embodiment, the invention comprises carbonylating methanol in a carbonylation system in the presence of a carbonylation catalyst under conditions effective to form acetic acid, hydrogenating the acetic acid in a hydrogenation system in the presence of a hydrogenation catalyst to form a crude ethanol product comprising ethanol and water, separating the ethanol from the water to form an ethanol stream and a water stream, and directing at least a portion of the water stream to the carbonylation system, e.g., for use in the carbonylation reaction medium.

Description

INTEGRATED PROCESS FOR PRODUCING ETHANOL FROM METHANOL

WITH WATER BALANCE CONTROL

FIELD OF THE INVENTION

[0001] The present invention relates generally to processes for producing ethanol. In particular, the invention relates to processes for producing ethanol from methanol via an acetic acid intermediate, in which water formed in the ethanol synthesis step is recycled to the acetic acid synthesis step to maintain the water balance in the carbonylation process.

BACKGROUND OF THE INVENTION

[0002] An important process for the production of acetic acid is the carbonylation of an alkyl alcohol, especially methanol, and reactive derivatives thereof, with carbon monoxide in a liquid reaction medium. In commercial processes, the carbonylation rate of reaction is strongly dependent on water concentrations, and thus it is important to maintain water levels in the reaction mixture during the production of acetic acid within controlled ranges to maintain high reaction rates. In some commercial processes, water is added to exert a beneficial effect upon the reaction rate and a water concentration of 14 to 15 wt.% are maintained as described in US Pat. No. 3,769,329. This is commonly referred to as a "high water" carbonylation process. In other "low water" carbonylation process, as described in US Pat. Nos. 5,001,259, 5,026,908, and 5, 144,068, water concentrations lower than 14 wt.% are used. In the low water

carbonylation process, water may be controlled in by optimizing the reaction conditions based on methanation reaction and water gas shift reaction, as described in US Pat. No. 7,005,541. Once water balance is controlled, either in a high or low water carbonylation process, when purifying acetic acid the water is continuously returned to the reaction medium to maintain the water balance. Upsets in the water balance may adversely affect the carbonylation reaction rate.

[0003] Integrated processes for forming ethanol from methanol, preferably through an acetic acid intermediate have been proposed in the literature. Generally, the acetic acid intermediate production produces glacial acetic acid that has less than 1500 wppni water by separating water from the acetic acid. For example, U.S. Pat. No. 7,884,253 discloses methods and apparatuses for selectively producing ethanol from syngas. The syngas is derived from cellulosic biomass (or other sources) and can be catalytically converted into methanol, which in turn can be catalytically converted into acetic acid or acetates. The ethanoic acid product may be removed from the reactor by withdrawing liquid reaction composition and separating the ethanoic acid product by one or more flash and/or fractional distillation stages from the other components of the liquid reaction composition such as iridium catalyst, aithenium and/or osmium and/or indium promoter, methyl iodide, water and unconsuiiied reactants which may be recycled to the reactor to maintain their concentrations in the liquid reaction composition.

[0004] EP2060553 discloses a process for the conversion of a carbonaceous feedstock to ethanol wherein the carbonaceous feedstock is first converted to ethanoic acid, which is then hydrogenated and converted into ethanol.

[0005] U.S. Pat. No. 4,497,967 discloses an integrated process for the preparation of ethanol from methanol, carbon monoxide and hydrogen feedstock. The process esterifies an acetic anhydride intermediate to form ethyl acetate and/or ethanol.

[0006] U.S. Pat. No. 7,351,559 discloses a process for producing ethanol including a combination of biochemical and synthetic conversions results in high yield ethanol production with concurrent production of high value co-products. An acetic acid intermediate is produced from carbohydrates, such as corn, using enzymatic milling and fermentation steps, followed by conversion of the acetic acid into ethanol using esterification and hydrogenation reactions.

[0007] As such, the need remains for improvements in the integration of acetic acid production and ethanol production.

SUMMARY OF THE INVENTION

[0008] The present invention is directed to integrated processes for forming ethanol from methanol, preferably through an acetic acid intermediate.

[0009] In one embodiment, the invention is to a process for producing a water stream. The process comprises the step of hydrogenating an acetic acid feed stream to form a caide ethanol product. The caide ethanol product preferably comprises ethanol, water, ethyl acetate, and acetic acid. The process further comprises the step of separating at least a portion of the caide ethanol product in at least one column into a distillate comprising ethanol and a residue comprising the water stream. The water is directed to an acetic acid production process, preferably for use in the reaction medium. [0010] In another embodiment, the invention is to a process for carbonylating methanol in a carbonylation system in the presence of a carbonylation catalyst under conditions effective to form acetic acid; hydrogenating the acetic acid in a hydrogenation system in the presence of a hydrogenation catalyst to form a caide ethanol product comprising ethanol and water;

separating the ethanol from the water to form an ethanol stream and a water stream; and directing at least a portion of the water stream to the carbonylation system.

[0011] In yet another embodiment, the invention is to a process for reacting carbon monoxide with at least one reactant in a first reactor containing a reaction medium to produce a reaction solution comprising acetic acid, wherein the at least one reactant is selected from the group consisting of methanol, methyl acetate, methyl formate, dimethyl ether and mixtures thereof and wherein the reaction medium comprises water, acetic acid, methyl iodide, and a first catalyst; hydrogenating the acetic acid in a hydrogenation system in the presence of a hydrogenation catalyst to form a caide ethanol product comprising ethanol and water, separating the ethanol from the water to form an ethanol stream and a water stream, and directing at least a portion of the water stream to the carbonylation system.

[0012] In yet another embodiment, the invention is to a process for producing a water stream, the process comprising providing a caide ethanol product comprising ethanol, water, ethyl acetate, and acetic acid, separating at least a portion of the caide ethanol product into an ethanol stream and a water stream, wherein the water stream is essentially free of organic impurities other than acetic acid, and directing at least a portion of the water stream to a carbonylation system.

BRIEF DESCRIPTION OF DRAWINGS

[0013] The invention is described in detail below with reference to the appended drawings, wherein like numerals designate similar parts.

[0014] FIG. 1 is a schematic diagram of an integrated system for forming ethanol from methanol via an acetic acid intermediate in accordance with one embodiment of the present invention.

[0015] FIG. 2 is a schematic diagram of an exemplary integrated carbonylation and hydrogenation process in accordance with one embodiment of the present invention. [0016] FIG. 3 is a schematic diagram of a hydrogenation process having four columns in accordance with an embodiment of the present invention.

[0017] FIG. 4 is a schematic diagram of another hydrogenation process having two columns with an intervening water separation in accordance with an embodiment of the present invention.

[0018] FIG. 5 is a schematic diagram of another hydrogenation process having two columns in accordance with an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

[0019] The present invention relates to integrated processes for making ethanol from methanol. In one embodiment, the process includes a step of carbonylating methanol in a carbonylation system in the presence of a carbonylation catalyst under conditions effective to form acetic acid. In one embodiment, some of the water in the acetic acid production is removed to reduce purification capital and/or energy requirements. However, removing the water with acetic acid may upset the water balance in the carbonylation process leading to reduction in carbonylation reaction rates. Reduced carbonylation reaction rates may further the efficiency in producing ethanol from methanol.

[0020] The acetic acid is subsequently hydrogenated in a hydrogenation system in the presence of a hydrogenation catalyst to form a caide ethanol product comprising ethanol and water. The caide ethanol product is separated into an ethanol stream and a water stream. At least a portion of the water stream is then directed back to the carbonylation system. The water balance in within the integrated process and particularly within the carbonylation reaction is maintained by using the water of reaction in the ethanol production process. In a preferred embodiment, the portion of the water stream from the ethanol production is recirculated back to the carbonylation system is regulated to maintain the water balance in the process.

Advantageously, embodiments of the present invention allow for reducing the energy required to purify the acetic acid without upsetting the water balance within the carbonylation process.

[0021] In one embodiment, the portion of the water stream directed back to the carbonylation system may be regulated based on the water concentration in the acetic acid stream from the carbonylation process. In-line analyzers may be used to measure the water concentration based on temperature, pressure, pH, density, etc. Based on this information, the flow of the water stream from the ethanol production may be regulated on a real-time basis. This may provide an active feedback that is responsive to water being removed from the carbonylation process. When water stream is not needed, the water stream may be directed to other processes such as hydrolysis reactors, scaibbers, extractive columns, or purged as necessary.

[0022] Water balance in the acetic acid production is typically maintained within tight windows to prevent upsets to the system. However, it is known that increases in water concentration lead to high production rates. Thus, in one embodiment, it may be preferred to return a larger portion of water from the ethanol production that removed in the acetic acid feed stream. Advantageously this may to increase carbonylation reaction rates and increase the efficiency of converting methanol to ethanol.

[0023] Although it may be preferred to return the water stream from the ethanol process directly to the carbonylation reactor, the water stream may be introduced into the carbonylation purification process. For example, the water stream may be introduced in the light ends overhead decanter. This may also assist in phasing the contents of the decanter.

[0024] In purifying the acetic acid to be fed to an ethanol production process, impurities such as methanol, methyl acetate, methyl formate, and/or dimethyl ether may be removed from the acetic acid fed to the ethanol production process. The presence of these components may cause additional alcohols to be formed in the ethanol production process that would lead to further separation costs to recovery ethanol. In addition, the presence of methanol, methyl acetate, methyl formate, and/or dimethyl in the ethanol production process may lead to the production of off-spec ethanol.

[0025] The acetic acid stream obtained from the carbonylation process may be fed through a hydrogenation reaction to produce a caide ethanol product comprising ethanol and water, generally in equal molar ratios. Due to the reduced purification, there may be more water in the acetic acid than would otherwise be present in industrial grade acetic acid. The increase water concentration may be removing water from the carbonylation process that would be needed to maintain the water balance. In addition, including water in the acetic acid feed stream would be expected to be detrimental to ethanol production because water is a co-product of the reaction and is not converted during hydrogenation. However, it has been found that feeding acetic acid and water in combination to a hydrogenation reactor does not substantially affect the conversion of acetic acid to ethanol and advantageously increases the efficiency of recovering ethanol from the resulting caide ethanol product.

[0026] The water balance may be upset by withdrawing water with the acetic acid. This may reduce the carbonylation reaction efficiency. In one embodiment, the acetic acid feed stream comprises water in amounts of up to 25 wt.%, e.g., up to 20 wt.% water, or up to 10 wt.% water. In terms of ranges the acetic acid feed stream may comprise from 0.15 wt.% to 25 wt.% water, e.g., from 0.2 wt.% to 20 wt.%, from 0.5 to 15 wt.%, or from 4 wt.% to 10. wt.%. In one embodiment, the acetic acid feed stream that is provided to the ethanol production process comprises water in an amount of at least 1500 wppni, e.g., at least 2500 wppni, at least 5000 wppni, or at least 1 wt.%. The remaining portion of the feed stream to the ethanol process preferably comprises acetic acid and hydrogen, preferably in a molar ratio of hydrogen to acetic acid 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. Most preferably, the molar ratio of hydrogen to acetic acid is greater than 2: 1, e.g., greater than 4: 1 or greater than 8: 1. In some embodiments, the acetic acid feed stream may also comprise other carboxylic acids and anhydrides, as well as optionally acetaldehyde and/or acetone. In particular, the acetic acid feed stream may comprise methyl acetate and/or propanoic acid. These other compounds may also be hydrogenated in the processes of the present invention.

[0027] Surprisingly and unexpectedly, the presence of water in amounts of up to 25 wt.% does not significantly reduce acetic acid conversion or selectivity to ethanol. For purposes of the present invention, the term "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. 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 of conversion. Although conversion and selectivity to ethanol may vary depending on the reaction conditions and catalyst, the presence of water does not result in significant variations to the acetic acid conversion or selectivity to ethanol.

[0028] In recovering ethanol, the caide ethanol product would be expected to comprise more water than would be produced from hydrogenating glacial acetic acid. The caide ethanol product preferably comprises from 5 to 70 wt.% ethanol, e.g., from 30 to 70 wt.% ethanol or from 45 to 70 wt.% ethanol, and from 5 to 60 wt.% water, e.g., from 15 to 60 wt.% water or from 20 to 60 wt.% water. Advantageously, having more water initially in the caide ethanol product may reduce the requirement to boil over water in the initial distillation column while recovering ethanol. Generally, the amount of water in the distillate from the initial distillation column may be closer to the azeotropic amount of water that forms with the ethanol/water azeotrope, preferably less than 20 wt.%, or less than 12 wt.%. Further separation of ethanol from the distillate may also be improved because of the reduced amounts of water. In one embodiment, the weight ratio of water in the residue to the water in the distillate is greater than 2: 1, e.g., greater than 4: 1 or greater than 6: 1. In some embodiments, particularly at higher conversions, the residue stream from the first distillation column may have a minor amount of acetic acid, e.g., less than 10 wt.%, or less than 5 wt.%, which allows the residue stream to be treated in a weak acid recovery system or sent to a reactive distillation column to convert the acid to esters.

[0029] The water stream returned to the carbonylation process preferably is substantially free of organics, except for acetic acid. Most of the organic impurities in the ethanol production contain more than two carbon atoms and these impurities may lead to produce of heavier components in the carbonylation process. Thus, it is particularly preferred to purifying the water stream while recovering ethanol so that the water stream may be returned to the carbonylation process.

[0030] FIG. 1 illustrates an integrated process 80 in accordance with one embodiment of the present invention. Process 80 comprises carbonylation system 82 and hydrogenation system 84. Carbonylation system 82 receives methanol feed 86 and carbon monoxide feed 88. The methanol and the carbon monoxide are reacted in carbonylation system 82 to form acetic acid. Carbonylation system 82, in some embodiments, further comprises a purification train comprising one or more distillation columns and/or extraction units (not shown in FIG. 1) to separate caide acetic acid into an acetic acid product stream 90 that also contains water.

[0031] Acetic acid product stream 90 is fed, more preferably directly fed, to hydrogenation system 84. Hydrogenation system 84 also receives hydrogen feed 92. In hydrogenation system 84, the acetic acid in acetic acid product stream 90 is hydrogenated to form a caide ethanol product comprising ethanol and other compounds such as water, ethyl acetate, and unreacted acetic acid. Hydrogenation system 84 further comprises one or more separation units, e.g., distillation columns and/or extraction units (not shown in FIG. 1.), for separately recovering ethanol and water from the caide ethanol product. An ethanol product stream 94 is then recovered from hydrogenation system 84. As shown, water that is recovered from the hydrogenation system is directed to the carbonylation system, as shown by water stream 96, where it may be used, for example, to maintain water to the carbonylation reaction.

[0032] In addition to integrating the water stream between the hydrogenation system 84 and carbonylation system 82, the process may also be integrated with methods for producing acetic acid and/or methods for producing methanol. For example, acetic acid may be produced from methanol, and thus ethanol production according to embodiments of the present invention may be produced from methanol. In one embodiment, the present invention comprises producing methanol from syngas, carbonylating the methanol to form acetic acid, and reducing acetic acid to form an alcohol, namely ethanol. In still another embodiment, the present invention comprises producing ethanol from a carbon source, such as coal, biomass, petroleum, or natural gas, by converting the carbon source to syngas, followed by converting the syngas to methanol, carbonylating the methanol to form acetic acid, and reducing acetic acid to form ethanol. In still another embodiment, the present invention comprises producing ethanol from a carbon source, such as coal, biomass, petroleum, or natural gas, by converting the carbon source to syngas, separating the syngas into a hydrogen stream and a carbon monoxide stream, carbonylating a methanol with the carbon monoxide stream to form acetic acid, and reducing acetic acid to form an ethanol. In addition, methanol may be produced from the syngas.

[0033] Various carbonylation systems and hydrogenation systems may be used in the processes of the present invention. Exemplary materials, catalysts, reaction conditions, and separation processes that may be used in the carbonylation and hydrogenation systems employed in the present invention are described further below.

Carbonylation System

[0034] In the carbonylation process, methanol is reacted with carbon monoxide in the presence of a carbonylation reactor under conditions effective to form acetic acid. In some embodiments, some or all of the raw materials for the carbonylation process may be derived partially or entirely from syngas. For example, 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. Similarly, hydrogen that is used in the step of hydrogenating the acetic acid to form the caide ethanol mixture, as described in further detail below, may be separated from syngas. The syngas, in turn, 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.

[0035] Examples of biomass 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, miscanthus, 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. Another biomass source is 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.

[0036] U.S. Pat. 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 carbonaceous materials to obtain a process gas which is steam pyrolized with additional natural gas to form synthesis gas. The syngas is converted to methanol which may be carbonylated to acetic acid. The method likewise produces hydrogen which may be used in connection with the hydrogenation system as noted above. U.S. Pat. No. 5,821, 1 1 1, which discloses a process for converting waste biomass through gasification into synthesis gas, and U.S. Pat. No. 6,685,754, which discloses a method for the production of a hydrogen-containing gas composition, such as a synthesis gas including hydrogen and carbon monoxide, are incorporated herein by reference in their entireties.

[0037] The carbonylation of methanol, or another carbonylatable reactant, including, but not limited to, methyl acetate, methyl formate, dimethyl ether, or mixtures thereof, to acetic acid preferably occurs in the presence of a Group VIII metal catalyst, such as rhodium, and a halogen-containing catalyst promoter. A particularly useful process is the low water rhodium- catalyzed carbonylation of methanol to acetic acid as exemplified in U.S. Pat. No. 5,001,259, the entirety of which is incorporated herein by reference.

[0038] Without being bound by theory, the rhodium component of the catalyst system is believed to be present in the form of a coordination compound of rhodium with a halogen component providing at least one of the ligands of such coordination compound. In addition to the coordination of rhodium and halogen, it is also believed that carbon monoxide will coordinate with rhodium. The rhodium component of the catalyst system may be provided by introducing into the reaction zone rhodium in the form of rhodium metal, rhodium salts such as the oxides, acetates, iodides, carbonates, hydroxides, chlorides, etc., or other compounds that result in the formation of a coordination compound of rhodium in the reaction environment.

[0039] The halogen-containing catalyst promoter of the catalyst system comprises a halogen compound, typically an organic halide. Thus, alkyl, aryl, and substituted alkyl or aryl halides can be used. Preferably, the halogen-containing catalyst promoter is present in the form of an alkyl halide. Even more preferably, the halogen-containing catalyst promoter is present in the form of an alkyl halide in which the alkyl radical corresponds to the alkyl radical of the feed alcohol, which is being carbonylated. Thus, in the carbonylation of methanol to acetic acid, the halide promoter will include methyl halide, and more preferably methyl iodide.

[0040] The liquid reaction medium employed may include any solvent compatible with the catalyst system and may include pure alcohols, or mixtures of the alcohol feedstock and/or the desired carboxylic acid and/or esters of these two compounds. A preferred solvent and liquid reaction medium for the low water carbonylation process contains the desired carboxylic acid product. Thus, in the carbonylation of methanol to acetic acid, a preferred solvent system contains acetic acid.

[0041] As discussed herein water in the reaction medium may have an impact on

carbonylation reaction rates. In one embodiment, the water concentration in the reaction medium may be at least about 14 wt.%. In other embodiments, the water concentration may be considerable lower, below 14 wt.% and as low as about 0.1 wt.%, preferably less than 2 wt.% water.

[0042] In accordance with the carbonylation process useful to manufacture acetic acid according to the present invention, the desired reaction rates are obtained even at low water concentrations by maintaining in the reaction medium an ester of the desired carboxylic acid and an alcohol, desirably the alcohol used in the carbonylation, and an additional iodide ion that is over and above the iodide ion that is present as hydrogen iodide. A desired ester is methyl acetate. The additional iodide ion is desirably an iodide salt, with lithium iodide being preferred. It has been found that under low water concentrations, methyl acetate and lithium iodide act as rate promoters only when relatively high concentrations of each of these components are present and that the promotion is higher when both of these components are present simultaneously. See, e.g., U.S. Pat. No. 5,001,259, incorporated herein by reference in its entirety. The concentration of iodide ion maintained in the reaction medium of the preferred carbonylation reaction system is believed to be quite high as compared with what little prior art there is dealing with the use of halide salts in reaction systems of this sort. The absolute concentration of iodide ion content is not a limitation on the usefulness of the present invention.

[0043] The carbonylation reaction of methanol to acetic acid product may be carried out by contacting the methanol feed with gaseous carbon monoxide bubbled through an acetic acid solvent reaction medium containing the rhodium catalyst, methyl iodide promoter, methyl acetate, and additional soluble iodide salt, at conditions of temperature and pressure suitable to form the carbonylation product. It will be generally recognized that it is the concentration of iodide ion in the catalyst system that is important and not the cation associated with the iodide, and that at a given molar concentration of iodide the nature of the cation is not as significant as the effect of the iodide concentration. Any metal iodide salt, or any iodide salt of any organic cation, or quaternary cation such as a quaternary amine or phosphine or inorganic cation can be maintained in the reaction medium provided that the salt is sufficiently soluble in the reaction medium to provide the desired level of the iodide. When the iodide is a metal salt, preferably it is an iodide salt of a member of the group consisting of the metals of Group IA and Group DA of the periodic table as set forth in the "Handbook of Chemistry and Physics" published by CRC Press, Cleveland, Ohio, 2002-03 (83rd edition). In particular, alkali metal iodides are useful, with lithium iodide being particularly suitable. In the low water carbonylation process which is useful in this invention, the additional iodide ion over and above the iodide ion present as hydrogen iodide is generally present in the catalyst solution in amounts such that the total iodide ion concentration is from about 2 to about 20 wt.% and the methyl acetate is generally present in amounts of from about 0.5 to about 30 wt.%, and the methyl iodide is generally present in amounts of from about 5 to about 20 wt.%. The rhodium catalyst is generally present in amounts of from about 200 to about 2000 parts per million (ppni).

[0044] Typical reaction temperatures for carbonylation will be from 150 to 250°C, with the temperature range of 180 to 220°C being a preferred range. The carbon monoxide partial pressure in the reactor can vary widely but is typically about 2 to about 30 atmospheres, and preferably, about 3 to about 10 atmospheres. Because of the partial pressure of by-products and the vapor pressure of the contained liquids, the total reactor pressure will range from about 15 to about 40 atmospheres.

[0045] In the carbonylation of methanol, PRC's such as acetaldehyde and PRC precursors may be formed as a byproduct, and as a result, the carbonylation system preferably includes a PRC Removal System (PRS) for removing such PRC's. PRC's may include, for example, compounds such as acetaldehyde, acetone, methyl ethyl ketone, butyraldehyde, crotonaldehyde, 2-ethyl crotonaldehyde, 2-ethyl butyraldehyde and the like, and the aldol condensation products thereof.

[0046] FIG. 2 shows exemplary integrated carbonylation and hydrogenation process 200, which comprises carbonylation system 202, hydrogenation zone 204, and hydrogenation separation zone 206. Carbonylation system 202 comprises 1) reaction zone 208, which comprises carbonylation reactor 210 and flasher 212, and 2) carbonylation separation zone 209, which comprises at least one distillation column, e.g., a light ends column and/or a drying column, 214, and phase separator, e.g., decanter, 216. Hydrogenation zone 204 comprises vaporizer 218 and hydrogenation reactor 220. Hydrogenation separation zone 206 comprises flasher 222 and column 224, also referred to as an "acid separation column." FIG. 3 is an exemplary hydrogenation zone with a hydrogenation separation zone having multiple columns.

[0047] In carbonylation system 202, methanol feed stream 226 comprises methanol and/or reactive derivatives thereof and carbon monoxide 228 are fed to a lower portion of

carbonylation reactor 210. Suitable reactive derivatives of methanol include methyl acetate, dimethyl ether, methyl formate, and mixtures thereof. At least some of the methanol and/or reactive derivative thereof will be converted to, and hence present as, methyl acetate in the liquid reaction composition by reaction with acetic acid product or solvent. The concentration in the liquid reaction composition of methyl acetate is suitably in the range of from 0.5 wt.% to 70 wt.%, e.g., from 0.5 wt.% to 50 wt.%, from 1 wt.% to 35 wt.%, or from 1 wt.% to 20 wt.%. [0048] Reactor 210 is preferably either a stirred vessel, e.g., CSTR, or bubble-column type vessel, with or without an agitator, within which the reaction medium is maintained, preferably automatically, at a predetermined level. This predetermined level may remain substantially constant during normal operation. Into reactor 210, methanol, carbon monoxide, and sufficient water may be continuously introduced as needed to maintain at least a finite concentration of water in the reaction medium.

[0049] Some or all of the water for the reaction medium is supplied from water recovered from the hydrogenation system. Stream 264 containing water separated from the ethanol product by the separation zone of the hydrogenation system is added to the carbonylation reactor 210. In an embodiment, the flow rate of stream 264 is measured and regulated to maintain water balance in the system. The flow rate can be measured by any method available, for example, using of an in-line measurement device such as a flow meter that can determine the water concentration. The flow rate of stream 264 can be added in combination with an outside source of water to the carbonylation reactor 210. If used, the flow rate of the outside source of water can also be adjusted to maintain water balance in the system or it can be fixed. Water can also be formed in situ in the reaction medium, for example, by the esterification reaction between methanol reactant and acetic acid product. In some embodiments, water is introduced to the reactor together with or separately from other components of the reaction medium. Post-reaction, water may be separated from the other components of reaction product withdrawn from the reactor and may be recycled in controlled amounts to maintain the required concentration of water in the reaction medium.

[0050] In one embodiment, carbon monoxide, e.g., in the gaseous state, is continuously introduced into reactor 210, desirably below an agitator, if presence, which is used to stir the contents. The temperature of reactor 210 may be controlled, as indicated above. Carbon monoxide feed 228 is introduced at a rate sufficient to maintain the desired total reactor pressure. [0051] The gaseous carbon monoxide feed is preferably thoroughly dispersed through the reaction medium. A gaseous purge is desirably vented via an off-gas line (not shown) from reactor 210 to prevent buildup of gaseous by-products, such as methane, carbon dioxide, and hydrogen, and to maintain a carbon monoxide partial pressure at a given total reactor pressure.

[0052] The caide acetic acid product is drawn off from the reactor 210 at a rate sufficient to maintain a constant level therein and is provided to flasher 212 via stream 232.

[0053] In flasher 212, the caide acetic acid product is separated in a flash separation step to obtain a volatile ("vapor") overhead stream 234 comprising acetic acid and a less volatile stream 236 comprising a catalyst-containing solution. The catalyst-containing solution comprises acetic acid containing the rhodium and the iodide salt along with lesser quantities of methyl acetate, methyl iodide, and water. The less volatile stream 236 preferably is recycled to reactor 210. Vapor overhead stream 234 also comprises methyl iodide, methyl acetate, water, and permanganate reducing compounds ("PRC's").

[0054] Overhead stream 234 from flasher 212 is directed to separation zone 209. Separation zone 209 comprises light ends column 214 and decanter 216. Separation zone 209 may also comprise additional units, e.g., a drying column, one or more columns for removing PRC's, heavy ends columns, extractors, etc.

[0055] In light ends column 214, stream 234 yields a low-boiling overhead vapor stream 238, a purified acetic acid stream that preferably is removed via a sidestreaiii 240, and a high boiling residue stream 242. Purified acetic acid that is removed via sidestreaiii 240 preferably is conveyed, e.g., directly, without removing substantially any water therefrom, to

hydrogenation system 204. Thus, the present invention provides for production efficiencies by using an acetic acid stream having a higher water content than glacial acetic acid, which beneficially reduces or eliminates the need for water removal downstream from light ends column 214 in carbonylation system 202.

[0056] In one embodiment, column 214 may comprise trays having different concentrations of water. In these cases, the composition of a withdrawn sidedraw may vary throughout the column. As such, the withdrawal tray may be selected based on the amount of water that is desired, e.g., more than 0.5 wt.%. In another embodiment, the configuration of the column may be varied to achieve a desired amount or concentration of water in a sidedraw. Thus, an acetic acid feed may be produced, e.g., withdrawn from a column, based on a desired water content. Accordingly, in one embodiment, the invention is to a process for producing ethanol comprising the step of withdrawing a purified acetic acid sidedraw from a light ends column in a carbonylation process, wherein a location from which the sidedraw is withdrawn is based on a water content of the sidedraw. The water content of the sidedraw may be from 0.15 wt.% to 25 wt.% water. The process further comprises the steps of hydrogenating acetic acid of the purified acetic acid stream in the presence of a catalyst under conditions effective to form a caide ethanol product comprising ethanol and water; and recovering ethanol from the caide ethanol product.

[0057] In another embodiment, the separation zone 209 comprises a second column, such as a drying column (not shown). A portion of the caide acetic acid stream 240 may be directed to the second column to separate some of the water from sidedraw 240 as well as other components such as esters and halogens. In these cases, the drying column may yield an acetic acid residue comprising acetic acid and from 0.15 wt.% to 25 wt.% water. The acetic acid residue exiting the second column may be fed to hydrogenation system 204 in accordance with the present invention.

[0058] The purified acetic acid stream, in some embodiments, comprises methyl acetate, e.g., in an amount ranging from 0.01 wt.% to 10 wt.% or from 0.1 wt.% to 5 wt.%. This methyl acetate, in preferred embodiments, may be reduced to form methanol and/or ethanol. In addition to acetic acid, water, and methyl acetate, the purified acetic acid stream may comprise halogens, e.g., methyl iodide, which may be removed from the purified acetic acid stream.

[0059] Returning to column 214, low-boiling overhead vapor stream 238 is preferably condensed and directed to an overhead phase separation unit, as shown by overhead receiver decanter 216. Conditions are desirably maintained in the process such that low-boiling overhead vapor stream 238, once in decanter 216, will separate into a light phase and a heavy phase. Generally, low-boiling overhead vapor stream 238 is cooled to a temperature sufficient to condense and separate the condensable methyl iodide, methyl acetate, acetaldehyde and other carbonyl components, and water into two phases. A gaseous portion of stream 238 may include carbon monoxide, and other noncondensable gases such as methyl iodide, carbon dioxide, hydrogen, and the like and is vented from the decanter 216 via stream 244.

[0060] Condensed light phase 246 from decanter 216 preferably comprises water, acetic acid, PRC's, as well as quantities of methyl iodide and methyl acetate. Condensed heavy phase 248 from decanter 216 will generally comprise methyl iodide, methyl acetate, and PRC's. The condensed heavy liquid phase 248, in some embodiments, be recirculated, either directly or indirectly, to reactor 210. For example, a portion of condensed heavy liquid phase 248 can be recycled to reactor 210, with a slip stream (not shown), generally a small amount, e.g., from 5 to 40 vol.%, or from 5 to 20 vol. %, of the heavy liquid phase being directed to a PRC removal system. This slip stream of heavy liquid phase 248 may be treated individually or may be combined with condensed light liquid phase 246 for further distillation and extraction of carbonyl impurities in accordance with one embodiment of the present invention.

Hydrogenation System

[0061] As discussed above, the processes of the invention integrate a carbonylation system with a hydrogenation system. The hydrogenation system preferably includes a hydrogenation reactor and a hydrogenation catalyst system effective in converting acetic acid to ethanol and water. The hydrogenation system also includes a separation system for separating a caide ethanol product into an ethanol product stream, a water stream (which is directed at least in part to the carbonylation system), and optionally one or more byproduct streams.

[0062] In addition to acetic acid, the acetic acid feed stream that is fed to the hydrogenation reactor may comprise other carboxylic acids and anhydrides, as well as aldehydes and/or ketones, such as acetaldehyde and acetone. Preferably, a suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These compounds may also be hydrogenated in the processes of the present invention. In some embodiments, the presence of some carboxylic acids, such as propanoic acid or its anhydride, may be beneficial in producing propanol. As described herein water is also present in the acetic acid feed.

[0063] 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. For reactions am in the vapor phase, the temperature should be controlled in the system such that it does not fall below the dew point of acetic acid. In one embodiment, 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. In another embodiment, the acetic acid is mixed with other gases before vaporizing, followed by heating the mixed vapors up to the reactor inlet temperature. Preferably, 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 reactor inlet temperature.

[0064] The reactor, in some embodiments, may include a variety of configurations using a fixed bed reactor or a fluidized bed reactor. In many embodiments of the present invention, 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. In other embodiments, a radial flow reactor or reactors may be employed as the reactor, or a series of reactors may be employed with or without heat exchange, quenching, or introduction of additional feed material. Alternatively, a shell and tube reactor provided with a heat transfer medium may be used. In many cases, the reaction zone may be housed in a single vessel or in a series of vessels with heat exchangers therebetween.

[0065] In preferred embodiments, 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. Other reactors, such as fluid or ebullient bed reactors, can be employed. In some instances, 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.

[0066] The hydrogenation in the reactor may be carried out in either the liquid phase or vapor phase. Preferably, 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. In terms of ranges 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" or from 1000 hr"1 to 6500 hr"1.

[0067] 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. [0068] Although 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. Most preferably, the molar ratio of hydrogen to acetic acid is greater than 2: 1, e.g., greater than 4: 1 or greater than 8: 1.

[0069] 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.

[0070] The hydrogenation of acetic acid to form ethanol is preferably conducted in the presence of a hydrogenation catalyst in the reactor. 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/ruthenium, cobalt/tin, silver/palladium, copper/palladium, copper/zinc, nickel/palladium, gold/palladium, ruthenium/rhenium, and ruthenium/iron. Exemplary catalysts are further described in U.S. Pat. No. 7,608,744 and U.S. Pub. No. 2010/0029995, the entireties of which are incorporated herein by reference. In another embodiment, 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.

[0071] In one embodiment, 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. Preferably, 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. In embodiments of the invention where the first metal comprises platinum, it is preferred that 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.

[0072] As indicated above, in some embodiments, the catalyst further comprises a second metal, which typically would function as a promoter. If present, 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.

[0073] In certain embodiments where the catalyst includes two or more metals, e.g., a first metal and a second metal, 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.%. For catalysts comprising two or more metals, the two or more metals may be alloyed with one another or may comprise a non-alloyed metal solution or mixture.

[0074] The preferred metal ratios may vary depending on the metals used in the catalyst. In some exemplary embodiments, 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.

[0075] 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. In preferred aspects, the third metal is selected from the group consisting of cobalt, palladium, aitheniuiii, copper, zinc, platinum, tin, and rhenium. More preferably, the third metal is selected from cobalt, palladium, and aitheniuiii. When present, 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.%.

[0076] In addition to one or more metals, in some embodiments of the present invention the catalysts further comprise a support or a modified support. As used herein, the term "modified support" refers to a support that includes a support material and a support modifier, which adjusts the acidity of the support material.

[0077] 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.%. In preferred embodiments that utilize a modified support, 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 throughout the support, layered throughout the support, coated on the outer surface of the support (i.e., egg shell), or decorated on the surface of the support.

[0078] As will be appreciated by those of ordinary skill in the art, 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.

[0079] 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 IIA 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.

[0080] As indicated, the catalyst support may be modified with a support modifier. In some embodiments, 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 Ti02, Zr02, Nb2Os, Ta2Os, Al20_3, B20_3, P2Os, and Sb20_3. Preferred acidic support modifiers include those selected from the group consisting of Ti02, Zr02, Nb2Os, Ta2Os, and Al203. The acidic modifier may also include those selected from the group consisting of WO3, M0O3, Fe203, CT2O3, V2O5, Mn02, CuO, C02O3, and Bi203.

[0081] In another embodiment, the support modifier may be a basic modifier that has a low volatility or no volatility. Such basic modifiers, for example, may be selected from the group consisting of: (i) alkaline earth metal 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. In addition to oxides and iiietasilicates, other types of modifiers including nitrates, nitrites, acetates, and lactates may be used. Preferably, 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 (CaSi03). If the basic support modifier comprises calcium metasilicate, it is preferred that at least a portion of the calcium metasilicate is in crystalline form.

[0082] 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 m2/g; median pore diameter of about 12 nni; average pore volume of about 1.0 cm3/g as measured by mercury intaision porosimetry and a packing density of about 0.352 g/cni3 (22 lb/ft3).

[0083] 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 H20/g support, a surface area of about 160 to 175 m2/g, and a pore volume of about 0.68 nil/g.

[0084] 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.

[0085] In particular, the hydrogenation of acetic acid may achieve favorable conversion of acetic acid and favorable selectivity and productivity to ethanol in the reactor. For purposes of the present invention, the term "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. For example, acetic acid may have a conversion that is greater than 40%, e.g., greater than 50%, greater than 70% or greater than 90%. The conversion may vary and may be from 40% to 70% in some embodiments and from 85% to 99% in others.

[0086] 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%. Preferably, the catalyst selectivity to ethoxylates is at least 60%, e.g., at least 70%, or at least 80%. As used herein, the term "ethoxylates" refers specifically to the compounds ethanol, acetaldehyde, and ethyl acetate. Preferably, in the reactor, 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.

[0087] The term "productivity," as used herein, refers to the grams of a specified product, e.g., ethanol, formed during the hydrogenation based on the kilograms of catalyst used per hour. A productivity of at least 100 grams of ethanol per kilogram of catalyst per hour, e.g., at least 400 grams of ethanol per kilogram of catalyst per hour or at least 600 grams of ethanol per kilogram of catalyst per hour, is preferred. In terms of ranges, 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.

[0088] 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. In terms of ranges, for large scale industrial production of ethanol, 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. Ethanol production from

fermentation, due the economies of scale, typically does not permit the single facility ethanol production that may be achievable by employing embodiments of the present invention.

[0089] In various embodiments of the present invention, the caide ethanol mixture produced by the reactor, before any subsequent processing, such as purification and separation, will typically comprise acetic acid, ethanol and water. Exemplary compositional ranges for the caide ethanol mixture are provided in Table 1. The "others" identified in Table 1 may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide.

TABLE 1

CRUDE ETHANOL MIXTURE COMPOSITIONS

Cone. Cone. Cone. Cone.

Component (wt.%) (wt.%) (wt.%) (wt.%)

Ethanol 5 to 70 15 to 70 15 to 50 25 to 50

Acetic Acid O to 90 O to 50 5 to 70 5 to 50

Water 5 to 60 15 to 60 20 to 60 20 to 40

Ethyl Acetate O to 30 O to 20 1 to 12 3 to 10

Acetaldehyde O to 10 O to 3 0.1 to 3 0.2 to 2

Diethyl Acetal 0.001 to 5 0.01 to 3 0.1 to 2 0.5 to 1.5

Others 0.1 to 10 0.1 to 6 0.1 to 4 —

[0090] In one embodiment, the crude ethanol mixture may comprise acetic acid in an amount less than 20 wt.%, e.g., less than 15 wt.%, less than 10 wt.% or less than 5 wt.%. In terms of ranges, the acetic acid concentration of Table 1 may range from 0.1 wt.% to 20 wt.%, e.g., 0.2 wt.% to 15 wt.%, from 0.5 wt.% to 10 wt.% or from 1 wt.% to 5 wt.%. In embodiments having lower amounts of acetic acid, the conversion of acetic acid is preferably greater than 75%, e.g., greater than 85% or greater than 90%. In addition, the selectivity to ethanol may also be preferably high, and is greater than 75%, e.g., greater than 85% or greater than 90%.

[0091] Continuing with Fig. 2, acetic acid sidedraw 240 from distillation column 214 of carbonylation process 202 is preferably directed to hydrogenation system 204. In one embodiment, the purified acetic acid stream may be sidestream 240 from a light ends column 214.

[0092] In hydrogenation system 204, hydrogen feed line 250 and sidedraw 240 comprising acetic acid and water is fed to vaporizer 218. Vapor feed stream 252 is withdrawn and fed to hydrogenation reactor 220. In one embodiment, lines 250 and 240 may be combined and jointly fed to the vaporizer 218. The temperature of vapor feed stream 252 is preferably from 100°C to 350°C, e.g., from 120°C to 310°C or from 150°C to 300°C. Vapor feed stream 252 comprises from 0.15 wt.% to 25 wt.% water. Any feed that is not vaporized is removed from vaporizer 218 via stream 254, as shown in FIG. 2, and may be recycled thereto or discarded. In addition, although FIG. 2 shows line 252 being directed to the top of reactor 220, line 252 may be directed to the side, upper portion, or bottom of reactor 220. Further modifications and additional components to reaction zone 204 are described below.

[0093] Reactor 220 contains the catalyst that is used in the hydrogenation of the carboxylic acid, preferably acetic acid. During the hydrogenation process, a caide ethanol product is withdrawn, preferably continuously, from reactor 220 via line 256 and directed to separation zone 206.

[0094] Separation zone 206 comprises flasher 222, and first column 224. Further columns may be included as need to further separate and purify the caide ethanol product as shown in FIG. 3. The caide ethanol product may be condensed and fed to flasher 222, which, in turn, provides a vapor stream and a liquid stream. Flasher 222 may operate at a temperature of from 20°C to 250°C, e.g., from 30°C to 250°C or from 60°C to 200°C. The pressure of flasher 222 may be from 50 kPa to 2000 kPa, e.g., from 75 kPa to 1500 kPa or from 100 kPa to 1000 kPa.

[0095] The vapor stream exiting flasher 222 may comprise hydrogen and hydrocarbons, which may be purged and/or returned to reaction zone 204 via line 258. As shown in FIG. 2, the returned portion of the vapor stream passes through compressor 260 and is combined with the hydrogen feed and co-fed to vaporizer 218.

[0096] The liquid from flasher 222 is withdrawn and pumped as a feed composition via line 262 to the side of column 224, which may be referred to as the first column when multiple columns are used as shown in FIG. 3. Column 224 may also be referred to as an "acid separation column." The contents of line 262 typically will be substantially similar to the product obtained directly from the reactor 220, and may, in fact, also be characterized as a caide ethanol product. However, the feed composition in line 262 preferably has substantially no hydrogen, carbon dioxide, methane or ethane, which are removed by flasher 222.

[0097] Optionally, the caide ethanol product may pass through one or more membranes to separate hydrogen and/or other non-condensable gases. In other optional embodiments, the caide ethanol product may be fed directly to the acid separation column as a vapor feed and the non-condensable gases may be recovered from the overhead of the column.

[0098] When the content of acetic acid in line 262 is less than 5 wt.%, acid separation column 224 may be skipped and line 262 may be introduced directly to a second column, e.g., a "light ends column." In addition, column 224 may be operated to initially remove a substantial portion of water as the residue.

[0099] In the embodiment shown in FIG. 2, line 262 is introduced in the lower part of first column 224, e.g., lower half or lower third. Depending on the acetic acid conversion and operation of column 224, unreacted acetic acid, water, and other heavy components, if present, are removed from the composition in line 262 and are withdrawn, preferably continuously, as residue. In preferred embodiments, the presence of larger amounts of water in line 262 allows separation of a majority of water in line 262 along with substantially all the acetic acid in residue stream 264. All or a portion of residue stream 264 may be recycled to reaction zone 204 as necessary to maintain the water concentration amounts for the acetic acid feed stream. In addition, residue stream 264 may be separated into a water stream and an acetic acid stream, and either stream may be returned to reaction zone 204. In other embodiments, residue stream 264 may be a dilute acid stream that may be treated in a weak acid recovery system or sent to a reactive distillation column to convert the acid to esters.

[0100] First column 224 also forms an overhead distillate, which is withdrawn via stream 266, 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. As indicated above, a majority of the water is withdrawn in residue via line 264 as opposed to distillate via line 266 such that the weight ratio of water in line 264 to line 266 is greater than 2: 1.

[0101] The columns shown in the FIGS, 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. In other embodiments, a packed column may be used. For packed columns, 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 and so on.

[0102] The associated condensers and liquid separation vessels that may be employed with each of the distillation columns may be of any conventional design. 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. Although one reactor and one flasher are shown in FIG. 2, additional reactors, flashers, condensers, heating elements, and other components may be used in various embodiments of the present invention. As will be recognized by those skilled in the art, various condensers, pumps, compressors, reboilers, dainis, 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.

[0103] The 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 superatomic 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.

[0104] When column 224 is operated under about 170 kPa, the temperature of the residue exiting in line 264 from column 224 preferably is from 90°C to 130°C, e.g., from 95°C to 120°C or from 100°C to 1 15°C. The temperature of the distillate exiting in line 266 from column 224 preferably is from 60°C to 90°C, e.g., from 65°C to 85°C or from 70°C to 80°C. In some embodiments, the pressure of first column 224 may range from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. For convenience, 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 constaied as requiring any particular separation order.

[0106] Some species, such as acetals, may decompose in column 224 such that very low amounts, or even no detectable amounts, of acetals remain in the distillate or residue. In addition, there may be an equilibrium reaction after the caide ethanol product exits reactor 220 in liquid feed 256. Depending on the concentration of acetic acid in the caide ethanol product, equilibrium may be driven toward formation of ethyl acetate. The reaction may be regulated using the residence time and/or temperature of liquid feed 256.

[0103] The distillate, e.g., overhead stream, of column 224 optionally is condensed and refluxed as shown in FIG. 2, preferably, at a reflux ratio of 1 :5 to 10: 1. The distillate in line 266 preferably comprises ethanol, ethyl acetate, and lower amounts of water. The separation of these species may be difficult, in some cases, due to the formation of binary and tertiary azeotropes.

[0104] In some embodiments, depending on acetic conversion and the amount of water withdrawn from column 244, distillate in line 266 may comprise a suitable ethanol product that requires no further processing.

[0105] In other embodiments, the first distillate in line 266 is further processed to remove byproducts.

[0106] Ethanol may be recovered using several different techniques. In FIG. 3, hydrogenation section separates the caide ethanol mixture using three columns 120, 123, 128 and/or an optional fourth column 131. In FIG. 4, the caide ethanol mixture is separated in two columns with an intervening water separation step. In FIG. 5, the separation of the caide ethanol mixture uses two columns. Other separation systems may also be used with embodiments of the present invention. For purposes of convenience, the columns in each exemplary separation process may be referred to as the first column, second column, third column, etc., but it should be understood that similarly named columns of the embodiments shown in FIGS. 3-5 will operate differently from one another.

[0107] In each of these FIGS. 3-5, hydrogenation system 100 includes a reaction zone 101 and a separation zone 102. Hydrogen and acetic acid are fed via lines 104 and 105, respectively, to a vaporizer 106 to create a vapor feed stream in line 107 that is directed to reactor 103. In one embodiment, lines 104 and 105 may be combined and jointly fed to vaporizer 106. The temperature of the vapor feed stream in line 107 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 106 and may be recycled thereto or discarded. In addition, although line 107 is shown as being directed to the top of reactor 103, line 107 may be directed to the side, upper portion, or bottom of reactor 103. [0108] Reactor 103 contains the catalyst that is used in the hydrogenation of the carboxylic acid, preferably acetic acid. In one embodiment, one or more guard beds (not shown) may be used upstream of the reactor, optionally upstream of vaporizer 106, 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. In one aspect, the guard bed media is functionalized, e.g., silver functionalized, to trap particular species such as sulfur or halogens. During the hydrogenation process, a caide ethanol mixture stream is withdrawn, preferably continuously, from reactor 103 via line 109.

[0109] The caide ethanol mixture stream in line 109 may be condensed and fed to a separator 1 10, which, in turn, provides a vapor stream 1 1 1 and a liquid stream 1 12. In some

embodiments, separator 1 10 may comprise a flasher or a knockout pot. The separator 1 10 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 1 10 may be from 50 kPa to 2000 kPa, e.g., from 75 kPa to 1500 kPa or from 100 kPa to 1000 kPa. Optionally, the caide ethanol mixture in line 109 may pass through one or more membranes to separate hydrogen and/or other non-condensable gases.

[0110] The vapor stream 1 1 1 exiting separator 1 10 may comprise hydrogen and hydrocarbons, and may be purged and/or returned to reaction zone 101. When returned to reaction zone 101, vapor stream 1 10 may be combined with the hydrogen feed 104 and co-fed to vaporizer 106. In some embodiments, the returned vapor stream 1 1 1 may be compressed before being combined with hydrogen feed 104.

[0111] In FIG. 3, the liquid stream 1 12 from separator 1 10 is withdrawn and pumped to the side of first column 120, also referred to as an "acid separation column." In one embodiment, the contents of liquid stream 1 12 are substantially similar to the caide ethanol mixture obtained from the reactor, except that the composition has been depleted of hydrogen, carbon dioxide, methane and/or ethane, which are removed by separator 1 10. Accordingly, liquid stream 1 12 may also be referred to as a caide ethanol mixture. Exemplary components of liquid stream 1 12 are provided in Table 2. It should be understood that liquid stream 1 12 may contain other components, not listed in Table 2. TABLE 2

COLUMN FEED COMPOSITION

(Liquid Stream 112)

Cone, (wt.%) Cone, (wt.%) Cone, (wt.%)

Ethanol 5 to 70 10 to 60 15 to 50

Acetic Acid < 90 5 to 80 5 to 70

Water 5 to 60 15 to 60 20 to 60

Ethyl Acetate < 30 0.001 to 20 1 to 12

Acetaldehyde < 10 0.001 to 3 0.1 to 3

Acetal < 5 0.001 to 2 0.005 to 1

Acetone < 5 0.0005 to 0.05 0.001 to 0.03

Other Esters < 5 < 0.005 < 0.001

Other Ethers < 5 < 0.005 < 0.001

Other Alcohols < 5 < 0.005 < 0.001

[0112] The amounts indicated as less than (<) in the tables throughout present specification are preferably not present and if present may be present in trace amounts or in amounts greater than 0.0001 wt.%.

[0113] 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 embodiment, the liquid stream 1 12 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.%. In should be understood that 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.

[0114] Optionally, crude ethanol mixture in line 109 or in liquid stream 1 12 may be further fed to an esterification reactor, hydrogenolysis reactor, or combination thereof. An esterification reactor may be used to consume residual acetic acid present in the caide ethanol mixture to further reduce the amount of acetic acid that would otherwise need to be removed.

Hydrogenolysis may be used to convert ethyl acetate in the caide ethanol mixture to ethanol.

[0115] In the embodiment shown in FIG. 3, line 1 12 is introduced in the lower part of first column 120, e.g., lower half or lower third. In first column 120, acetic acid, a portion of the water, and other heavy components, if present, are removed from the composition in line 121 and are withdrawn, preferably continuously, as residue. Some or all of the residue may be returned and/or recycled back to reaction zone 101 via line 121. Recycling the acetic acid in line 121 to the vaporizer 106 may reduce the amount of heavies that need to be purged from vaporizer 106. Reducing the amount of heavies to be purged may improve efficiencies of the process while reducing byproducts.

[0116] First column 120 also forms an overhead distillate, which is withdrawn in line 122, 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. The distillate in line 122 comprises primarily ethanol, as well as water, ethyl acetate, acetaldehyde, and/or diethyl acetal. For example, distillate may comprise from 20 to 75 wt.% ethanol and 10 to 40 wt.% ethanol. Preferably, the concentration of acetic acid in the distillate is less than 2 wt.%, e.g., less than 1 wt.% or less than 0.5 wt.%.

[0117] In one embodiment, first column 120 may be operated at ambient pressure. In other embodiments, the pressure of first column 120 may range from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. When first column 120 is operated under standard atmospheric pressure, the temperature of the residue exiting in line 121 preferably is from 95°C to 120°C, e.g., from 1 10°C to 1 17°C or from 1 1 1°C to 1 15°C. The temperature of the distillate exiting in line 122 preferably is from 70°C to 1 10°C, e.g., from 75°C to 95°C or from 80°C to 90°C.

[0118] As shown, the first distillate in line 122 is introduced to the second column 123, also referred to as the "light ends column," preferably in the middle part of column 123. Preferably the second column 123 is an extractive distillation column, and an extraction agent is added thereto via lines 124 and/or 125. 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. In preferred embodiments, the extraction agent is comprised primarily of water. As indicated above, the first distillate in line 122 that is fed to the second column 123 comprises ethanol, water, and ethyl acetate. These compounds tend to form binary and ternary azeotropes, which decrease separation efficiency. As shown, in one embodiment the extraction agent comprises the third residue in line 124. Preferably, the recycled third residue in line 124 is fed to second column 123 at a point higher than the first distillate in line 122. In one embodiment, the recycled third residue in line 124 is fed near the top of second column 123 or fed, for example, above the feed in line 122 and below the reflux line from the condensed overheads. In a tray column, the third residue in line 124 is continuously added near the top of the second column 123 so that an appreciable amount of the third residue is present in the liquid phase on all of the trays below. In another embodiment, the extraction agent is fed from a source outside of the process 100 via line 125 to second column 123. Preferably this extraction agent comprises water.

[0119] 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. In terms of ranges, 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.

[0120] In one embodiment, an additional extraction agent, such as water from an external source, dimethylsulfoxide, glycerine, diethylene glycol, 1-naphthol, hydroquinone, Ν,Ν'- diiiiethylformamide, 1,4-butanediol; ethylene glycol-l,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, Ν,Ν'-diiiiethylethylenediaiiiine, diethylene triamine, hexamethylene diamine and 1,3- diaminopentane, an alkylated thiopene, dodecane, tridecane, tetradecane and chlorinated paraffins, may be added to second column 123. Some suitable extraction agents include those described in U.S. Patent Nos. 4,379,028, 4,569,726, 5,993,610 and 6,375,807, the entire contents and disclosure of which are hereby incorporated by reference. The additional extraction agent may be combined with the recycled third residue in line 124 and co-fed to the second column 123. The additional extraction agent may also be added separately to the second column 123. In one aspect, the extraction agent comprises an extraction agent, e.g., water, derived from an external source via line 125 and none of the extraction agent is derived from the third residue.

[0121] Second column 123 may be a tray or packed column. In one embodiment, second column 123 is a tray column having from 5 to 120 trays, e.g., from 15 to 80 trays or from 20 to 70 trays. The temperature of second column 123 at atmospheric pressure may vary. Second column 123 may operate at a pressure ranging from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. In one embodiment second residue exiting in line 126 preferably is at a temperature 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 127 from second column 123 preferably is from 50°C to 90°C, e.g., from 60°C to 80°C or from 60°C to 70°C.

[0122] The second residue in line 126 comprises ethanol and water. The second residue may comprise less than 3 wt.% ethyl acetate, e.g., less than 1 wt.% ethyl acetate or less than 0.5 wt.% ethyl acetate. The second distillate in line 127 comprises ethyl acetate, acetaldehyde, and/or diethyl acetal. In addition, minor amounts of ethanol may be present in the second distillate. 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.

[0123] 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 at which point a portion of the third residue may be recycled with the remaining portion 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. As the third residue is recycled, the composition of the second residue comprises less than 30 wt.% of ethanol, e.g., less than 20 wt.% or less than 15 wt.%. The majority of the second residue preferably comprises water. Notwithstanding this effect, 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.

[0124] As shown, the second residue from second column 123, which comprises ethanol and water, is fed via line 126 to third column 128, also referred to as the "product column." More preferably, the second residue in line 126 is introduced in the lower part of third column 128, e.g., lower half or lower third. Third column 128 recovers ethanol, which preferably is substantially pure with respect to organic impurities and other than the azeotropic water content, as the distillate in line 129. The distillate of third column 128 preferably is refluxed as shown in FIG. 3, 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 124, which comprises primarily water can be returned to the second column 123 as an extraction agent. Preferably, this third residue is substantially free of ethanol. In one embodiment, a first portion of the third residue in line 124 is recycled to the second column and a second portion returned to the carbonylation process via line 130. In one embodiment, once the process reaches steady state, the second portion of water returned to the carbonylation process is substantially similar to the amount of water formed in the hydrogenation of acetic acid. In one embodiment, a portion of the third residue may be used to hydrolyze any other stream, such as one or more streams comprising ethyl acetate. In one embodiment, the third residue in line 124 is withdrawn from third column 128 at a temperature higher than the operating temperature of the second column 123. Preferably, the third residue in line 124 is integrated to heat one or more other streams or is reboiled prior to be returned to the second column 123.

[0125] Although FIG. 3 show the third residue being directly recycled to second column 123, 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).

[0126] Third column 128 is preferably a tray column. In one embodiment, third column 128 may operate at a pressure from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. At atmospheric pressure, the temperature of the third distillate exiting in line 129 preferably is from 60°C to 1 10°C, e.g., from 70°C to 100°C or from 75°C to 95°C. The temperature of the third residue in line 124 preferably is from 70°C to 1 15°C, e.g., from 80°C to 1 10°C or from 85°C to 105°C.

[0127] Any of the compounds that are carried through the distillation process from the feed or caide 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.%. In one embodiment, one or more side streams may remove impurities from any of the columns in the system 100. Preferably at least one side stream is used to remove impurities from the third column 128. The impurities may be purged and/or retained within the system 100. The composition of the ethanol product obtained from the third distillate in FIG. 3 is shown below in Table 3.

[0128] The third distillate in line 129 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, adsorption units, membranes, or molecular sieves. Suitable adsorption units include pressure swing adsorption units and thermal swing adsorption unit.

[0129] Returning to second column 123, the second distillate preferably is refluxed as shown in FIG. 3, 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 in line 127 may be purged or recycled to the reaction zone. The second distillate in line 127 may be further processed in an optional fourth column 131, also referred to as the "acetaldehyde removal column." In optional fourth column 131, the second distillate is separated into a fourth distillate, which comprises acetaldehyde, in line 132 and a fourth residue, which comprises ethyl acetate, in line 133. 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. For example, the fourth distillate may be combined with the acetic acid feed, added to the vaporizer 106, or added directly to the reactor 103. The fourth distillate preferably is co-fed with the acetic acid in feed line 105 to vaporizer 106. Without being bound by theory, since 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. In another embodiment, 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 crotonaldehyde and derivatives.

[0130] The fourth residue of optional fourth column 131 may be purged via line 133. 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. In one preferred embodiment, the acetaldehyde is removed from the second distillate in fourth column 131 such that no detectable amount of acetaldehyde is present in the residue of column 131.

[0131] Optional fourth column 131 is preferably a tray column as described above and preferably operates above atmospheric pressure. In one embodiment, 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. In a preferred embodiment the fourth column 131 may operate at a pressure that is higher than the pressure of the other columns. [0132] The temperature of the fourth distillate exiting in line 132 preferably is from 60°C to 1 10°C, e.g., from 70°C to 100°C or from 75°C to 95°C, The temperature of the residue in line 133 preferably is from 70°C to 1 15°C, e.g., from 80°C to 1 10°C or from 85°C to 1 10°C.

[0133] In one embodiment, a portion of the third residue in line 124 is recycled to second column 123. In one embodiment, recycling the third residue further reduces the aldehyde components in the second residue and concentrates these aldehyde components in second distillate in line 127 and thereby sent to the fourth column 131, wherein the aldehydes may be more easily separated. The third distillate, e.g. intermediate stream, in line 129 may have lower concentrations of aldehydes and esters due to the recycling of third residue in line 124.

[0134] Although the composition of the third residue may vary depending on the specific separation conditions, in preferred embodiments the third residue comprises water and may be referred to herein as a water stream. Exemplary compositions for the third distillate and third residue (water stream) are provided below in Table 3. It should also be understood that the distillate may also contain other components, not listed, such as components in the feed.

TABLE 3

THIRD COLUMN

Cone, (wt.%) Cone, (wt.%) Cone, (wt.%)

Distillate

Ethanol 75 to 96 80 to 96 85 to 96

Water < 12 l to 9 3 to 8

Acetic Acid < 1 0.001 to 0.1 0.005 to 0.01

Ethyl Acetate < 5 0.001 to 4 0.01 to 3

Residue (Water Stream)

Water 97 to 100 98 to 100 99 to 100

Ethanol < 0.005 < 0.002 < 0.001

Ethyl Acetate < 0.001 < 0.0005 not detectable

Acetic Acid < 0.5 < 0.1 < 0.05

Organic Impurities < 0.001 < 0.0005 not detectable

[0135] As shown in FIG. 3, all or a portion of the third residue stream is directed to the carbonylation system, e.g., as shown in FIG. 2, for example to serve in the reaction medium for the carbonylation reaction. This third residue stream may have an acidic pH, preferably between 2.99 and 3.35. [0136] FIG. 4 illustrates another exemplary separation system that has a similar reaction zone 101 as FIG. 3 and produces a liquid stream 1 12, e.g., caide ethanol mixture, for further separation. In one preferred embodiment, the reaction zone 101 of FIG. 4 operates at above 70% acetic acid conversion, e.g., above 85% conversion or above 90% conversion. Thus, the acetic acid concentration in the liquid stream 1 12 may be low.

[0137] Liquid stream 1 12 is fed to the first column 134 to yield a first distillate 135 and first residue 136. Liquid stream 1 12 may be introduced in the middle or lower portion of first column 134, also referred to as acid-water column. In one embodiment, no entrainers are added to first column 134. Water and acetic acid, along with any other heavy components, if present, are removed from liquid stream 1 12 and are withdrawn, preferably continuously, as a first residue in line 136. Preferably, a substantial portion of the water in the caide ethanol mixture that is fed to first column 134 may be removed in the first residue, for example, up to about 75% or to about 90% of the water from the caide ethanol mixture. In one embodiment, 30 to 90% of the water in the caide ethanol mixture is removed in the residue, e.g., from 40 to 88% of the water or from 50 to 84% of the water.

[0138] When first column 134 is operated under about 170 kPa, the temperature of the residue exiting in line 136 preferably is from 90°C to 130°C, e.g., from 95°C to 120°C or from 100°C to 1 15°C. The temperature of the distillate exiting in line 135 preferably is from 60°C to 90°C, e.g., from 65°C to 85°C or from 70°C to 80°C. In some embodiments, the pressure of first column 134 may also range from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa.

[0139] The first distillate in line 135 comprises some water in addition to ethanol and other organics. In terms of ranges, the water concentration in the first distillate in line 135 preferably is from 4 wt.% to 38 wt.%, e.g., from 7 wt.% to 32 wt.%, or from 7 to 25 wt.%. A portion of first distillate in line 137 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. It is understood that reflux ratios may vary with the number of stages, feed locations, column efficiency and/or feed composition. Operating with a reflux ratio of greater than 3 : 1 may be less preferred because more energy may be required to operate the first column 134. The condensed portion of the first distillate may also be fed to a second column 138. [0140] As shown, the remaining portion of the first distillate in line 139 is fed to a water separation unit 140. Water separation unit 140 may be an adsorption unit, membrane, molecular sieves, extractive column distillation, or a combination thereof. A membrane or an array of membranes may also be employed to separate water from the distillate. The membrane or array of membranes may be selected from any suitable membrane that is capable of removing a permeate water stream from a stream that also comprises ethanol and ethyl acetate.

[0141] In a preferred embodiment, water separator 140 is a pressure swing adsorption (PSA) unit. The PSA unit is optionally 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 kPa to 150 kPa. The PSA unit may comprise from two to five beds. Water separator 140 may remove at least 95% of the water from the portion of first distillate in line 139, and more preferably from 99% to 99.99% of the water from the first distillate, in a water stream 141. All or a portion of water stream 141 may be returned to first column 134 in line 142, where the water preferably is ultimately recovered from column 134 in the first residue in line 136. Additionally or alternatively, all or a portion of water stream 141 may be removed from the hydrogenation system via line 143. The remaining portion of first distillate exits the water separator 140 as ethanol mixture stream 144. Ethanol mixture stream 144 may have a low water concentration of less than 10 wt.%, e.g., less than 6 wt.% or less than 2 wt.%.

[0142] In this aspect of the invention, either or both the first residue in line 136 and/or the separated stream in line 143 comprise water and may be referred to as a water stream.

Preferably, these streams are substantially free of ethanol. Exemplary compositions for line 136 and line 143 are provided in Table 4, below. It should also be understood that these streams may also contain other components, not listed, such as components derived from the feed.

TABLE 4

WATER STREAMS IN FIG. 4

Cone, (wt.%) Cone, (wt.%) Cone, (wt.%)

First Residue 136

Acetic Acid < 90 1 to 50 2 to 35

Water 30 to 100 45 to 95 60 to 90

Ethanol < 1 < 0.9 < 0.3

Water Stream 143

Water 80 to 100 85 to 99.5 90 to 99

Ethanol < 10 0.001 to 5 0.01 to 0.5

Ethyl Acetate < 10 0.001 to 5 0.01 to 0.5

[0143] In one embodiment, all or a portion of either or both the first residue in line 136 and/or the separated stream in line 143 may be directed to the carbonylation system, e.g., as shown in FIG. 2, to maintain water balance in the reaction medium. In a preferred

embodiment, all or a portion of the first residue and/or line 143 is directed to the carbonylation system to serve in the reaction medium for the carbonylation reaction.

[0144] Preferably, ethanol mixture stream 144 is not returned or refluxed to first column 135. The condensed portion of the first distillate in line 137 may be combined with ethanol mixture stream 144 to control the water concentration fed to the second column 138. For example, in some embodiments the first distillate may be split into equal portions, while in other embodiments, all of the first distillate may be condensed or all of the first distillate may be processed in the water separation unit. In FIG. 4, the condensed portion in line 137 and ethanol mixture stream 144 are co-fed to second column 138. In other embodiments, the condensed portion in line 137 and ethanol mixture stream 144 may be separately fed to second column 138. The combined distillate and ethanol mixture has a total water concentration of greater than 0.5 wt.%, e.g., greater than 2 wt.% or greater than 5 wt.%. In terms of ranges, the total water concentration of the combined distillate and ethanol mixture may be from 0.5 to 15 wt.%, e.g., from 2 to 12 wt.%, or from 5 to 10 wt.%.

[0145] The second column 138 in FIG. 4, also referred to as the "light ends column," removes ethyl acetate and acetaldehyde from the first distillate in line 137 and/or ethanol mixture stream 144. Ethyl acetate and acetaldehyde are removed as a second distillate in line 145 and ethanol is removed as the second residue in line 146. Preferably ethanol is recovered with low amounts of ethyl acetate, acetaldehyde, and/or acetal, e.g., less than 1 wt.% or more preferably less than 0.5 wt.%. The ethanol product obtained from second residue in FIG. 4, is shown below in Table 6. Preferably, the ethanol product comprises less than 1 wt.% diethyl acetal, e.g., less than 0.5 wt.% or less than 0.01 wt.%.

[0146] Second column 138 may be a tray column or packed column. In one embodiment, second column 138 is a tray column having from 5 to 120 trays, e.g., from 15 to 100 trays or from 20 to 90 trays. In one embodiment, second column 138 operates at a pressure from 101 kPa to 5,000 kPa, e.g., from 120 kPa to 4,000 kPa, or from 150 kPa to 3,000 kPa. In other embodiments, second column 138 may operate at a pressure ranging from 0.1 kPa to 510 kPa, e.g., from 10 kPa to 450 kPa or from 50 kPa to 350 kPa. Although the temperature of second column 138 may vary, when at about 20 kPa to 70 kPa, the temperature of the second residue exiting in line 146 preferably is from 30°C to 75°C, e.g., from 35°C to 70°C or from 40°C to 65°C . The temperature of the second distillate exiting in line 145 preferably is from 20°C to 55°C, e.g., from 25°C to 50°C or from 30°C to 45°C.

[0147] The total concentration of water fed to second column 138 preferably is less than 10 wt.%, as discussed above. When first distillate in line 137 and/or ethanol mixture stream 144 comprises minor amounts of water, e.g., less than 1 wt.% or less than 0.5 wt.%, additional water may be fed to the second column 138 as an extractive agent in the upper portion of the column. A sufficient amount of water is preferably added via the extractive agent such that the total concentration of water fed to second column 138 is from 1 to 10 wt.% water, e.g., from 2 to 6 wt.%, based on the total weight of all components fed to second column 138. If the extractive agent comprises water, the water may be obtained from an external source or from an internal return/recycle line from one or more of the other columns or water separators.

[0148] Suitable extractive agents may also include, for example, dimethylsulfoxide, glycerine, diethylene glycol, 1-naphthol, hydroquinone, N,N'-diiiiethylforiiiaiiiide, 1,4- butanediol; ethylene glycol-l,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, Ν,Ν'- dimethylethylenediamine, diethylene triamine, hexamethylene diamine and 1,3- diaminopentane, an alkylated thiopene, dodecane, tridecane, tetradecane, chlorinated paraffins, or a combination thereof. When extractive agents are used, a suitable recovery system, such as a further distillation column, may be used to recycle the extractive agent.

[0149] The second distillate in line 145, which comprises ethyl acetate and/or acetaldehyde, preferably is refluxed as shown in FIG. 4, for example, at a reflux ratio of from 1 :30 to 30: 1, e.g., from 1 : 10 to 10: 1 or from 1 :3 to 3: 1. In one aspect, not shown, the second distillate 145 or a portion thereof may be returned to reactor 103.

[0150] In one embodiment, the second distillate in line 145 and/or a refined second distillate, or a portion of either or both streams, may be further separated to produce an acetaldehyde- containing stream and an ethyl acetate-containing stream. For example, the optional fourth column 131 of FIG. 3 may be used to separate second distillate in line 145. This may allow a portion of either the resulting acetaldehyde-containing stream or ethyl acetate-containing stream to be recycled to reactor 103 while purging the other stream. The purge stream may be valuable as a source of either ethyl acetate and/or acetaldehyde. In one embodiment, it may be preferred to operate second column 138 in FIG. 4 at a pressure less than atmospheric pressure to decrease the energy required to separate ethyl acetate and ethanol.

[0151] Another exemplary two column separation scheme is shown in FIG. 5. In this embodiment, liquid stream 1 12 is introduced in the upper part of first column 160, e.g., upper half or upper third. In one embodiment, no entrainers are added to first column 160. In first column 160, a weight majority of the ethanol, water, acetic acid, and other heavy components, if present, are removed from liquid stream 1 12 and are withdrawn, preferably continuously, as the first residue in line 162. First column 160 also forms an overhead distillate, which is withdrawn in line 161, 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 first distillate in line 161 preferably comprises a weight majority of the ethyl acetate from liquid line 1 12. In addition, distillate in line 161 may also comprise acetaldehyde.

[0152] When column 160 is operated under about 170 kPa, the temperature of the residue exiting in line 162 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 160 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, at 170 kPa, of the distillate exiting in line 161 preferably is from 75°C to 100°C, e.g., from 75°C to 83°C or from 81°C to 84°C. [0153] In one embodiment, column 160 of FIG. 5 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 162 to water in the distillate in line 161 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.

[0154] The amount of acetic acid in the first residue 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.%.

[0155] The distillate preferably is substantially free of acetic acid, e.g., comprising less than 1000 wppni, less than 500 wppni or less than 100 wppni acetic acid. The distillate may be purged from the system or recycled in whole or part to reactor 103. In some embodiments, the distillate may be further separated, e.g., in an optional fourth column of FIG. 3, 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.

[0156] To recover ethanol, the residue in line 162 may be further separated in a second column 163, also referred to as an "acid separation column." An acid separation column may be used 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 162 is introduced to second column 163 preferably in the top part of column 163, e.g., top half or top third. Second column 163 yields a second residue in line 165 comprising acetic acid and water, and a second distillate in line 164 comprising ethanol.

[0157] Second column 163 may be a tray column or packed column. In one embodiment, second column 163 is a tray column having from 5 to 150 trays, e.g., from 15 to 50 trays or from 20 to 45 trays. In some embodiments, the second column 163 of FIG. 5 is operated at a pressure ranging from 0.1 kPa to 510 kPa, e.g., from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. In the system shown in FIG. 5, it is preferred to operate the first column 160 at an increased pressure, because second column 163 comprises very low amounts of acetaldehyde and/or acetals. At atmospheric pressure the temperature of the second residue exiting in line 165 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 164 preferably is from 60°C to 105°C, e.g., from 75°C to 100°C or from 80°C to 100°C.

[0158] The weight ratio of ethanol in the second distillate in line 164 to ethanol in the second residue in line 165 preferably is at least 35: 1. In one embodiment, the weight ratio of water in the second residue 165 to water in the second distillate 164 is greater than 2: 1, e.g., greater than 4: 1 or greater than 6: 1. In addition, the weight ratio of acetic acid in the second residue 165 to acetic acid in the second distillate 164 preferably is greater than 10: 1, e.g., greater than 15: 1 or greater than 20: 1. Preferably, the second distillate in line 164 is substantially free of acetic acid and may only contain, if any, trace amounts of acetic acid. Preferably, the second distillate in line 164 contains substantially no ethyl acetate.

[0159] The remaining water from the second distillate in line 164 may be removed in further embodiments of the present invention. Depending on the water concentration, the ethanol product may be derived from the second distillate in line 164. Some applications, such as industrial ethanol applications, may tolerate water in the ethanol product, while other applications, such as fuel applications, may require an anhydrous ethanol. The amount of water in the distillate of line 164 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 may be removed from the second distillate in line 164 using several different separation techniques as described herein. Particularly preferred techniques include the use of distillation column, membranes, adsorption units, and combinations thereof.

[0160] In one embodiment of the invention, the second residue 165 comprises primarily water and may be referred to as a water stream. Preferably stream 165 is substantially free of ethanol. Exemplary compositions for second residue 165 are provided in Table 5, below.

TABLE 5

EXEMPLARY COMPOSITIONS FOR WATER STREAM 165 IN FIG. 5

Cone, (wt.%) Cone, (wt.%) Cone, (wt.%)

Acetic Acid 0.1 to 45 0.2 to 40 0.5 to 35

Water 45 to 100 55 to 99.8 65 to 99.5

Ethyl Acetate <2 <1 <0.5

Ethanol <5 0.001 to 5 <2 [0161] In one embodiment, all or a portion of the second residue 165 is directed to a carbonylation system to maintain water balance in the reaction medium for the carbonylation reaction.

[0162] In one embodiment, any of the residue streams from FIGS. 3-5 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 acetic 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 optionally is returned to the reactor 103. The resulting water stream may be directed to a carbonylation system as discussed above.

[0163] In other embodiments, for example, where the second residue comprises less than 50 wt.% acetic acid, possible options include one or more of: (i) neutralizing the acetic acid, or (ii) reacting the acetic acid with an alcohol. 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-C12 alkanes. When neutralizing the acetic acid, it is preferred that the residue comprises less than 10 wt.% acetic acid. Acetic acid may be neutralized with any suitable alkali or alkaline earth metal base, such as sodium hydroxide or potassium hydroxide. When reacting acetic acid with an alcohol, it is preferred that the residue comprises less than 50 wt.% acetic 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. Preferably, the alcohol comprises ethanol and the resulting ester comprises ethyl acetate. Optionally, the resulting ester may be fed to the hydrogenation reactor.

[0164] The columns shown in figures may comprise any distillation column capable of performing the desired separation and/or purification. For example, other than the acid columns describe above, the other columns preferably are 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. In other embodiments, a packed column may be used. For packed columns, 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.

[0165] 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. Although 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. As will be recognized by those skilled in the art, various condensers, pumps, compressors, reboilers, dainis, 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.

[0166] The temperatures and pressures employed in the columns may vary. 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.

[0167] The final ethanol product produced by the processes of the present invention may be taken from a stream that primarily comprises ethanol from exemplary systems shown in the figures. The ethanol product 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 6.

TABLE 6

FINISHED ETHANOL COMPOSITIONS

Component Cone, (wt.%) Cone, (wt.%) Cone, (wt.%)

Ethanol 75 to 99.9 80 to 99.5 85 to 96

Water < 12 l to 9 3 to 8

Acetic Acid < 1 < 0.1 < 0.01

Ethyl Acetate < 2 < 0.5 < 0.05

Diethyl Acetal < 1 0.0001 to 0.1 0.0001 to 0.01

Acetone < 0.05 < 0.01 < 0.005

Isopropanol < 0.5 < 0.1 < 0.05

n-propanol < 0.5 < 0.1 < 0.05

[0168] 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 C4-C20 alcohols. In one embodiment, 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. In one embodiment, 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.

[0169] In some embodiments, when further water separation is used, the ethanol product may be withdrawn as a stream from the water separation unit as discussed above. In such embodiments, the ethanol concentration of the ethanol product may be greater than indicated in Table 6, and preferably is greater than 97 wt.% ethanol, e.g., greater than 98 wt.% or greater than 99.5 wt.%. The ethanol product in this aspect preferably comprises less than 3 wt.% water, e.g., less than 2 wt.% or less than 0.5 wt.%.

[0170] 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. In fuel applications, the finished ethanol composition may be blended with gasoline for motor vehicles such as automobiles, boats and small piston engine aircraft. In non- fuel applications, 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.

[0171] 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, ethylamines, ethyl benzene, aldehydes, butadiene, and higher alcohols, especially butanol. In the production of ethyl acetate, the finished ethanol composition may be esterified with acetic acid. In another application, 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 entire contents and disclosures of which are hereby incorporated by reference. A zeolite catalyst, for example, may be employed as the dehydration catalyst. Preferably, the zeolite has a pore diameter of at least about 0.6 nni, 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. 2,882,244 and zeolite Y in U.S. Pat. No. 3, 130,007, the entireties of which are hereby incorporated herein by reference.

[0172] While the invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those of skill in the art. In addition, it should be understood that aspects of the invention and portions of various embodiments and various features recited above and/or in the appended claims may be combined or interchanged either in whole or in part. In the foregoing descriptions of the various embodiments, those embodiments which refer to another embodiment may be appropriately combined with other embodiments as will be appreciated by one of skill in the art. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.

Claims

We claim:
1. A process for producing ethanol, the process comprising the steps of:
reacting carbon monoxide with at least one reactant in a carbonylation system containing a reaction medium to produce a reaction solution comprising acetic acid, wherein the at least one reactant is selected from the group consisting of methanol, methyl acetate, methyl formate, dimethyl ether and mixtures thereof and wherein the reaction medium comprises water, acetic acid, methyl iodide, and a carbonylation catalyst;
purifying the reaction solution to obtain an acetic acid stream comprising acetic acid and water;
hydrogenating the acetic acid in a hydrogenation system in the presence of a
hydrogenation catalyst to form a caide ethanol product; separating the caide ethanol product to yield an ethanol stream and a water stream; and
directing a portion of the water stream to the carbonylation system.
2. The process of claim 1, wherein the water concentration in the reaction medium is less than 2 wt.%.
3. The process of claim 1, wherein a water balance for the carbonylation system is maintained.
4. The process of claim 3, wherein the water balance is maintained by regulating the aliquot portion of the water stream that is directed to the carbonylation system based on the concentration of water in the acetic acid stream.
5. The process of claim 4, further comprising measuring water concentration of the acetic acid stream.
6. The process of claim 1, wherein the water stream is essentially free of organic impurities other than acetic acid.
7. The process of claim 1, wherein the water stream comprises:
at least 97 wt.% water; and
less than 0.5 wt.% acetic acid.
8. The process of claim 1, wherein the water stream has a pH ranging from 2.99 to 3.35.
9. The process of claim 1, wherein the acetic acid stream comprises substantially no methanol, methyl acetate, methyl formate, or dimethyl ether.
10. The process of claim 1, wherein the acetic acid stream comprises less than 0.01 wt.% of methanol, methyl acetate, methyl formate, or dimethyl ether.
1 1. The process of claim 1, wherein the separating comprises:
separating at least a portion of the caide ethanol product in a first column into a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising water; 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 the water stream.
12. The process of claim 1 1, wherein the second column is an extractive distillation column.
13. The process of claim 12, wherein at least a portion of the water stream is directed to the second column.
14. The process of claim 1, wherein the hydrogenation catalyst comprises a combination of metals selected from the group consisting of platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, platinum/tin, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/aithenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium, and aithenium/iron.
15. The process of claim 1, wherein the separating comprises:
separating at least a portion of the caide ethanol product in a first column into a first distillate comprising ethyl acetate, acetaldehyde and ethanol, and a first residue comprising water and acetic acid, wherein the water stream that is directed to the carbonylation system is an aliquot or non-aliquot portion of the first residue.
16. The process of claim 1, wherein the separating comprises:
separating at least a portion of the caide ethanol product in a first column into a first distillate comprising ethyl acetate, acetaldehyde and ethanol, and a first residue comprising water and acetic acid, wherein the aliquot portion of the water stream that is directed to the carbonylation system is derived from the first residue.
17. The process of claim 16, wherein the first distillate further comprises water and the process further comprises the step of removing water from the first distillate, wherein at least a portion of the removed water is directed to the carbonylation system.
18. The process of claim 1, wherein the separating comprises:
separating at least a portion of the caide ethanol product in a first column into a first distillate comprising ethyl acetate, and acetaldehyde, and a first residue comprising ethanol, water and acetic acid,
separating at least a portion of the first residue in a second column into a second distillate comprising ethanol and a second residue comprising water and acetic acid, wherein the aliquot portion of the water stream that is directed to the carbonylation system is derived from the second residue.
PCT/US2011/060012 2011-11-09 2011-11-09 Iintegrated process for producing ethanol from methanol with water balance control WO2013070213A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2011/060012 WO2013070213A1 (en) 2011-11-09 2011-11-09 Iintegrated process for producing ethanol from methanol with water balance control

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2011/060012 WO2013070213A1 (en) 2011-11-09 2011-11-09 Iintegrated process for producing ethanol from methanol with water balance control

Publications (1)

Publication Number Publication Date
WO2013070213A1 true WO2013070213A1 (en) 2013-05-16

Family

ID=45048253

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/060012 WO2013070213A1 (en) 2011-11-09 2011-11-09 Iintegrated process for producing ethanol from methanol with water balance control

Country Status (1)

Country Link
WO (1) WO2013070213A1 (en)

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3130007A (en) 1961-05-12 1964-04-21 Union Carbide Corp Crystalline zeolite y
US3769329A (en) 1970-03-12 1973-10-30 Monsanto Co Production of carboxylic acids and esters
US4379028A (en) 1982-03-30 1983-04-05 Lloyd Berg Separation of ethyl acetate from ethanol and water by extractive distillation
US4497967A (en) 1984-06-15 1985-02-05 The Halcon Sd Group, Inc. Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen
US4569726A (en) 1984-07-19 1986-02-11 Lloyd Berg Process for the separation of ethyl acetate from ethanol and water by extractive distillation
US5001259A (en) 1984-05-03 1991-03-19 Hoechst Celanese Corporation Methanol carbonylation process
US5026908A (en) 1984-05-03 1991-06-25 Hoechst Celanese Corporation Methanol carbonylation process
US5144068A (en) 1984-05-03 1992-09-01 Hoechst Celanese Corporation Methanol carbonylation process
USRE35377E (en) 1993-05-27 1996-11-12 Steinberg; Meyer Process and apparatus for the production of methanol from condensed carbonaceous material
US5821111A (en) 1994-03-31 1998-10-13 Bioengineering Resources, Inc. Bioconversion of waste biomass to useful products
US5993610A (en) 1998-05-04 1999-11-30 Berg; Lloyd Separation of ethyl acetate from ethanol by azeotropic distillation
US6375807B1 (en) 1999-01-28 2002-04-23 Izak Nieuwoudt Separation of ethanol mixtures by extractive distillation
US6685754B2 (en) 2001-03-06 2004-02-03 Alchemix Corporation Method for the production of hydrogen-containing gaseous mixtures
US20040122257A1 (en) * 2002-12-23 2004-06-24 Hosea Cheung Low water methanol carbonylation process for high acetic acid production and for water balance control
US20070270511A1 (en) * 2006-04-05 2007-11-22 Woodland Chemical Systems Inc. System and method for converting biomass to ethanol via syngas
US7351559B2 (en) 1999-03-11 2008-04-01 Zeachem, Inc. Process for producing ethanol
EP2060553A1 (en) 2007-11-14 2009-05-20 BP p.l.c. Process for the conversion of hydrocarbons into alcohol
US7608744B1 (en) 2008-07-31 2009-10-27 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US20100030002A1 (en) 2008-07-31 2010-02-04 Johnston Victor J Ethylene production from acetic acid utilizing dual reaction zone process
US20100030001A1 (en) 2008-07-31 2010-02-04 Laiyuan Chen Process for catalytically producing ethylene directly from acetic acid in a single reaction zone
US20100197485A1 (en) 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethanol from acetic acid
US7863489B2 (en) 2008-07-31 2011-01-04 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US7884253B2 (en) 2008-12-11 2011-02-08 Range Fuels, Inc. Methods and apparatus for selectively producing ethanol from synthesis gas
US20110082322A1 (en) * 2008-07-31 2011-04-07 Radmila Jevtic Process for Making Ethanol From Acetic Acid Using Acidic Catalysts

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3130007A (en) 1961-05-12 1964-04-21 Union Carbide Corp Crystalline zeolite y
US3769329A (en) 1970-03-12 1973-10-30 Monsanto Co Production of carboxylic acids and esters
US4379028A (en) 1982-03-30 1983-04-05 Lloyd Berg Separation of ethyl acetate from ethanol and water by extractive distillation
US5001259A (en) 1984-05-03 1991-03-19 Hoechst Celanese Corporation Methanol carbonylation process
US5144068A (en) 1984-05-03 1992-09-01 Hoechst Celanese Corporation Methanol carbonylation process
US5026908A (en) 1984-05-03 1991-06-25 Hoechst Celanese Corporation Methanol carbonylation process
US4497967A (en) 1984-06-15 1985-02-05 The Halcon Sd Group, Inc. Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen
US4569726A (en) 1984-07-19 1986-02-11 Lloyd Berg Process for the separation of ethyl acetate from ethanol and water by extractive distillation
USRE35377E (en) 1993-05-27 1996-11-12 Steinberg; Meyer Process and apparatus for the production of methanol from condensed carbonaceous material
US5821111A (en) 1994-03-31 1998-10-13 Bioengineering Resources, Inc. Bioconversion of waste biomass to useful products
US5993610A (en) 1998-05-04 1999-11-30 Berg; Lloyd Separation of ethyl acetate from ethanol by azeotropic distillation
US6375807B1 (en) 1999-01-28 2002-04-23 Izak Nieuwoudt Separation of ethanol mixtures by extractive distillation
US7351559B2 (en) 1999-03-11 2008-04-01 Zeachem, Inc. Process for producing ethanol
US6685754B2 (en) 2001-03-06 2004-02-03 Alchemix Corporation Method for the production of hydrogen-containing gaseous mixtures
US7005541B2 (en) 2002-12-23 2006-02-28 Celanese International Corporation Low water methanol carbonylation process for high acetic acid production and for water balance control
US20040122257A1 (en) * 2002-12-23 2004-06-24 Hosea Cheung Low water methanol carbonylation process for high acetic acid production and for water balance control
US20070270511A1 (en) * 2006-04-05 2007-11-22 Woodland Chemical Systems Inc. System and method for converting biomass to ethanol via syngas
EP2060553A1 (en) 2007-11-14 2009-05-20 BP p.l.c. Process for the conversion of hydrocarbons into alcohol
US7608744B1 (en) 2008-07-31 2009-10-27 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US20100030002A1 (en) 2008-07-31 2010-02-04 Johnston Victor J Ethylene production from acetic acid utilizing dual reaction zone process
US20100030001A1 (en) 2008-07-31 2010-02-04 Laiyuan Chen Process for catalytically producing ethylene directly from acetic acid in a single reaction zone
US20100197485A1 (en) 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethanol from acetic acid
US7863489B2 (en) 2008-07-31 2011-01-04 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US20110082322A1 (en) * 2008-07-31 2011-04-07 Radmila Jevtic Process for Making Ethanol From Acetic Acid Using Acidic Catalysts
US7884253B2 (en) 2008-12-11 2011-02-08 Range Fuels, Inc. Methods and apparatus for selectively producing ethanol from synthesis gas

Similar Documents

Publication Publication Date Title
US9024087B2 (en) Process for making ethanol from acetic acid using acidic catalysts
EP2531467B1 (en) Process for recovering ethanol
US8575403B2 (en) Hydrolysis of ethyl acetate in ethanol separation process
US8304586B2 (en) Process for purifying ethanol
US8394985B2 (en) Process for producing an ester feed stream for esters production and co-production of ethanol
US8318988B2 (en) Process for purifying a crude ethanol product
US20120010445A1 (en) Low Energy Alcohol Recovery Processes
US8884080B2 (en) Reduced energy alcohol separation process
US9024083B2 (en) Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed
US8846988B2 (en) Liquid esterification for the production of alcohols
CN103068782B (en) Process for removing water from ethanol mixtures
CN103080053B (en) Use stacked bed reactor for producing ethanol
US8829250B2 (en) Finishing reactor for purifying ethanol
CN102918012B (en) The method for producing ethanol
KR20120086717A (en) Process for making ethanol from acetic acid using acidic catalysts
AU2011213058B2 (en) Process for purifying a crude ethanol product
WO2011097220A2 (en) Process for producing ethanol using an extractive distillation column
US8653308B2 (en) Process for utilizing a water stream in a hydrolysis reaction to form ethanol
CN102791665B (en) Hydrogenolysis of ethyl alcohol separation process
US8884081B2 (en) Integrated process for producing acetic acid and alcohol
US8680342B2 (en) Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US20130131400A1 (en) Hydrogenating Acetic Acid to Produce Ethyl Acetate and Reducing Ethyl Acetate to Ethanol
WO2012039839A1 (en) Production of alcohols
CN103221367B (en) Extractive distillation of the crude alcohol product
CN103080054B (en) The method of using a plurality of beds of different catalysts, respectively, to produce ethanol

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11788691

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11788691

Country of ref document: EP

Kind code of ref document: A1