TW201247300A - Using a dilute acid stream as an extractive agent - Google Patents

Abstract

Recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid using an extractive distillation column. A diluted acid stream, comprising less than 30 wt.% acetic acid, is used as the extractive agent and is fed at a point above the crude feed stream. The column yields a residue that comprises ethanol, acetic acid, and water. The diluted acid stream may be separated from the residue and returned to the extractive distillation column.

Description

201247300 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: * VI. Description of the invention: Cross-Reference to Related Applications This application claims US Patent Application No. 61/566,435, filed on Dec. 2, 2011. Priority. This application is also related to U.S. Patent Application Serial No. 13/094,588, filed on Apr. 26, 2011, and U.S. Patent No. 62,034, filed on Jun. 16, 2011. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a process for producing ethanol from acetic acid in a hydrogenation reactor, and more particularly to an extractive distillation process for recovering ethanol using a dilute acid stream. [Prior Art] Industrial ethanol is conventionally produced from organic sources such as petroleum, natural gas or coal, or from source intermediates such as syngas or from starchy materials or cellulosic materials such as corn or sugar cane. Conventional methods for producing ethanol from organic sources and from cellulosic materials include ethylene acid catalyzed hydration, methanol homologation, direct alcohol synthesis, and ^scher-Tropsch synthesis. The unstable price of petrochemical sources will cause the price of ethanol produced by the float to be more volatile, which will make the alternative energy source for ethanol production more demanding when the source price increases. The starchy material and the cellulose material are converted into ethanol by fermentation. However, fermentation is generally used in the manufacture of > xiaofei ethanol, whereby the ethanol produced is suitable for fuel or human consumption. In addition, fermentation of the secret or cellulosic material competes with the food source and limits the amount of ethanol that can be made for industrial use. Various combinations of catalysts, supports, and operating conditions have been described in the literature for the production of ethanol via the reduction of sulphuric acids and/or other carbonyl-containing compounds. In the county thief, such as the county, the company will form other compounds with ethanol or form other compounds in the side reaction. The impurities limit the production and recovery of ethanol from this reaction mixture. For example, during hydrogenation, it will only be produced together with ethanol and/or water, and it will be difficult to separate. Furthermore, when the conversion is incomplete, the unreacted acid will remain in the crude ethanol product, which must be removed to recover the ethanol. EP 0 206 G553 describes a method for the conversion of nicotinol to acetic acid which comprises converting the flue to acetic acid and hydrogenating the acetic acid to ethyl SI. The reduction from the hydrogenation retort is separated to obtain a stream of ethanol and a stream of acetic acid and ethyl acetate which will be recycled to the hydrogenation reactor. * US Pat. No. 7,842,844 describes a method for the conversion of hydrocarbons to ethanol and optionally acetic acid in the presence of a particulate catalyst, improved selectivity and catalytic activity and operational lifetime, which is produced via syngas The intermediate steps are carried out. Others have proposed various extractants for separating a mixture of ethanol, ethyl acetate and water. U.S. Patent No. 4,654,123 describes a process for separating ethanol from water using an extractant. U.S. Patent Nos. 4,379,028 and 4,569,726 describe the use of an extractant to recover ethyl acetate from an ethyl acetate/ethanol/water mixture. U.S. Patent No. 6,375,8,7 describes the use of an extractant to separate ethanol and ethyl acetate. There is still a need for an improved process for recovering ethanol from crude products obtained by reduction of alkanoic acids such as acetic acid and/or other carbonyl containing compounds. SUMMARY OF THE INVENTION In a first embodiment, the invention relates to a process for producing ethanol comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form a crude ethanol product; in the first column Separating at least a portion of the crude ethanol product into a first distillate comprising acetaldehyde and ethyl acetate, and a first residue comprising ethanol, ethyl acetate, water, and acetic acid; a dilute acid stream comprising less than 30% by weight (wt%) acetic acid or less than 5% by weight acetic acid introduced into the first column at a point above the crude ethanol product; and recovering ethanol from the first residue . In one embodiment, the dilute acid stream further comprises water having a water concentration of at least about the concentration of water in the crude ethanol product. The process further includes separating the first residue into an ethanol product and a dilute acid stream. In a second embodiment, the invention relates to a process for the manufacture of ethanol comprising: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form a crude ethanol product; at least part of the crude in a 201247300 tower The ethanol product is separated into a first distillate comprising ethyl acetate in ethyl acetate, and a first residue comprising ethanol, ethyl acetate, water and acetic acid; and the dilute acid is fed to a scale higher than the crude ethanol product. Leading to the first column; separating the residue in the second column, including the second distillation of ethanol and - and the second residue including money ^; returning at least a portion of the second residue to the first a column; and recovering ethanol from the distillate. ° u - In a third embodiment, the present invention is directed to a process for producing ethanol comprising: hydrogenating acetic acid from an acetic acid feed stream in a reactor, and forming the ethanol into the first % at least in part The crude ethanol product is separated into a first product comprising: the acetic acid (10) and a first product comprising ethanol, acetic acid, water and acetic acid; and the dilute acid is fed to the feed point of the crude ethanol product. Introduced to the first column; the second residue is separated in the second column to produce a second material comprising ethanol and acetic acid, and the water I is less than 30% (the second residue of acetic acid) Returning at least a portion of the ruthenium residue to the first column as - or a plurality of extractants; and recovering ethanol from the second take-up product. In a specific example, the process further includes at least a portion of the second Separating the product to produce a third distillate comprising ethyl acetate and a third residue comprising ethanol. In a fourth embodiment, the invention relates to a process for producing ethanol, which comprises: providing crude ethanol, The first-tower towel separates at least a portion of the miscellaneous material into乙骏和乙乙为的第一似' and the first residue containing ethanol, acetic acid (10), water and acetic acid; the spur stream is introduced to the first tower above the feed point of the miscellaneous ethanol yarn And recovering ethanol from the first residue. [Embodiment] The present invention relates to a process for recovering ethanol obtained by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction comprises obtaining ethanol, water, acetic acid, The crude ethyl acetate 4-acid B, acetic acid and other impurities are separated by a mixture of ethyl acetate and ethanol, and the acetic acid is the light phase of ethanol. The presence of other components such as acetic acid, acetic acid, and (iv) may further complicate the separation of ethanol and ethyl acetate depending on the concentration. 201247300 In order to improve the efficiency of recovering ethanol from the crude ethanol product, the process of the present invention involves the use of One or more extractants recover ethanol from the crude ethanol product in the first (first) column. The ethanol 'water and acetic acid are extracted as a residue. Ethyl acetate and other light organic matter are extracted as an extract. The presence of the extractant Efficiently separating the ethanol product from the acetic acid by-product by the use of an extractant such that a substantial portion of the ethyl acetate can be recovered from the crude ethanol product. Preferably, the first derivative is obtained. Recovering at least 90% of the ethyl acetate in the crude ethanol product, such as at least 95% ethyl acetate or at least 98% ethyl acetate. A major amount of ethyl acetate is recovered to provide a low concentration of acetic acid to the residue from the initial column.乙酉的', if less than 1 weight ° / 〇 (wt%), less than 0.3wt% or less 〇.〇lwt〇 / 〇e by using one or more extractants 'recoverable with reduced ethyl acetate content Preferably, the at least 50 〇/〇 ethanol, and more preferably at least 90% ethanol, of the crude ethanol product is recovered in the first residue stream. Advantageously, the separation process using the extractant results in The reduced energy requirement for recovering ethanol from the crude ethanol product. The extractant used in the present invention may vary. Preferably, the extractant has a boiling point higher than that of the main component of the drug. In a preferred embodiment, the extractant used has a higher than 8 Torr. The boiling point of bismuth, such as above 85 ° C or above 100. (: has a boiling point higher than 200. (The extractant may also be considered herein. Preferably, the extractant comprises water. Water may be produced in the hydrogenation reactor and recycled as an extractant. Preferably, At least one extracting agent is a co-product of ethanol produced by hydrogenating acetic acid. By using an extracting agent as a co-product, the extraction agent recovery and recovery cost can be reduced. In the case of Xingfujia, the co-product water can be unnecessary. A portion of the deliberately purified dilute acid stream. Although not limited herein, a dilute acid stream may be preferred when the hydrogenation achieves a high acetic acid conversion of greater than 80%, greater than 90%, or greater than 95%. The dilute acid stream can reduce the overall energy demand while maintaining efficient separation in the initial column. The dilute acid stream can include at least 40 wt% water, such as at least 60 wt% water or at least 8 wt% water. In one embodiment, the dilute acid stream Included is a water concentration at least about equal to the concentration of water in the crude ethanol product. The dilute acid stream can include acetic acid. For example, the dilute acid extractant can include less than 3 〇 milk % acetic acid, such as less than 2 〇%, Less than 10% by weight or less than 5% by weight. When expressed in terms of range, the dilute acid stream may include from 〇1 to 201247300 3〇wm acetic acid, such as 〇·5(4)_. Without being bound by theory, although acetic acid may not necessarily act as an extractant', it may reduce the carrying of two or two. The amount of ethanol, water and/or acetic acid, the common product is water and the water is purified by removing ethanol and / or B & purifying the water can reduce its system may lead to the tower Other components of the side reaction ^. The water ageable moisture material element, such as a single-domain membrane, dissipates the unit of the reaction, and the water can be returned to the acetic acid of the reactor. Other suitable county agents may also be used with the dilute acid stream-domain, and may include, for example, dimethyl ketone: glycerin, diethylene glycol 'naphthoquinone, hydroquinone, hydrazine, hydrazine, dimethyl Amarylamine, I-alcohol, ethylene glycol-1,5-pentanediol, propylene glycol], butadiene glycol, B-, formic acid methyl vinegar, cyclohexyl, hydrazine, Ν'-dimethyl-1, 3·propylenediamine, hydrazine, hydrazine, _dimethylethylenediamine, diethylenetriamine, hexamethylenetriamine, diamine sister, burnt porphin, twelve courtyards, thirteen burns, ten Four burning, chlorine The other extracts can be used with the effluent. Some suitable extractants include those described in U.S. Patent No. 4,379, 〇28; 4,5, 726; Μ%, (10) and 6,375,8 The same is incorporated herein by reference in its entirety. The towel picker is fed and mixed with the crude ethanol product prior to being introduced into the original column. Preferably, most of the ethanol, water and acetic acid are used as the residue from the initial column from the crude ethanol. Product removal. The residual stream may, for example, comprise from 30% to 99.5% water and from 85% to 100% acetic acid from the crude ethanol product. The residual liquid stream may include an extractant, water, and thus the water concentration in the residue may exceed the water concentration of the crude ethanol product. The extractant can be recovered from the residue in one or more additional separation columns and recycled to the initial column. Typically, the feed from the initial column may include ethyl acetate and acetaldehyde. This distillate may be recycled to the hydrogenation reactor in whole or in part. In some embodiments, the distillate from the initial column may also comprise ethanol and preferably less than 15% by weight water, less than 75% by weight water, less than 4% by weight water or less than 2% by weight water. An additional extraction column can be used to remove ethanol from the distillate. In other specific examples, a light hydrocarbon column (li# ends c〇lumn) can be used to separate the distillate into an ethyl acetate stream and an ethanol stream in a step of 201247300, and the ethyl acetate stream is recycled. In the hydrogenation reactor. While the specific examples of the present invention generally reduce the amount of ethyl acetate in the residue, ethyl acetate may still be present due to further esterification. Preferably, any ethyl acetate in the residue is separated to produce a purified ethanol solution >, IL. The separation column may be necessary if the residue comprises at least 5 ppm by weight (Wppm) of ethyl acetate, or if esterified. When ethyl acetate is less than 50 wppm', it is not necessary to use a separation column to separate ethyl acetate and ethanol. Ethyl acetate separated from the residue can be returned to the initial column and removed as the first distillate. The returned ethyl acetate stream can be fed into the initial column below the extractant feed point. The process of the present invention can be used with any hydrogenation process for making ethanol. The materials, catalysts, reaction conditions and separation processes which can be used in the weathering of acetic acid are detailed as follows. β The raw materials used in the process of the invention, acetic acid and hydrogen, can be derived from any suitable source, including natural gas, petroleum, coal rot, raw materials, etc. . For example, acetic acid can be produced by decyl alcoholization, ethylene oxidation, ethane oxidation, oxidative fermentation, and anaerobic fermentation. Methanolation processes suitable for the manufacture of acetic acid are described in U.S. Patent Nos. 7,208,624; 7,115,772; 7,005,541; 6,657,078; 6,627,770; 6,143,930; 5,599,976; 5,144, 068; 5, 026, 908, 5, 001, 259, and 4,994, 608, the entire disclosures of each of . Ethanol production can be integrated with the methanol carbonylation process, as appropriate. As oil and natural gas prices become expensive or cheaper, methods for producing acetic acid and intermediates such as sterols and carbon monoxide from other carbon sources are gaining attention. In particular, it is advantageous to produce acetic acid from a synthesis gas (, syngas,) derived from other available carbon sources when the petroleum is relatively expensive. A method for improving the manufacture of a methanol plant for acetic acid is taught, for example, in U.S. Patent No. 6,232,352, the entire disclosure of which is incorporated herein by reference. By improving the methanol plant, the significant cost associated with the production of carbon monoxide (C0) in the new acetic acid plant can be significantly reduced or largely eliminated. All or part of the syngas is derived from the sterol synthesis pathway and is supplied to a separator unit to recover carbon monoxide, which is then used to make acetic acid. In a similar manner, hydrogen can be supplied from the syngas. In some embodiments, some or all of the raw materials of the above-described acetic acid deuteration process may be partially bitten. 201247300 is all derived from syngas. For example, acetic acid can be formed from decyl alcohol and carbon monoxide, both derived from syngas. The syngas can be formed by partial oxidation reforming or steam reforming, and carbon monoxide can be separated from the syngas. Similarly, the hydrogen used in the step of hydrogenating acetic acid to form a crude ethanol product can be separated from the syngas. This syngas can in turn be derived from a variety of carbon sources. The carbon source may, for example, be selected from the group consisting of natural gas, gasoline, petroleum, coal, biomass materials, and combinations thereof. Syngas or hydrogen can also be obtained from biologically derived decane gases such as biologically derived decane gas produced by waste burial or agricultural waste. Syngas derived from biomass material will have a detectable 14C isotope content compared to fossil fuels such as coal or natural gas. The carbon nucleus of carbon forms a balance between constant new formation and degraded degradation in the Earth's atmosphere, and therefore the proportion of MC in the carbon nucleus in the Earth's atmosphere is constant over the long term. Since the living organic system is present in the surrounding atmosphere, the proportion of the 14c:12c nucleus of the same distribution ratio is established in the living organism, and stops changing when it dies, and the MC decomposes with a half-life of about 6,000 years. The methanol, acetic acid and/or ethanol formed from the syngas derived from the syngenetic material is expected to have a uc content substantially similar to that of the living organism. For example, 14C: 12 of methanol, acetic acid, and/or ethanol (the ratio may be one to a half of the ratio of mc: 丨7 of the living organism to about 1. In other specific examples, the syngas, methanol, acetic acid, and/or described herein. Ethanol is derived entirely from fossil fuels, that is, more than 6 〇, the carbon source produced two years ago, without the detectable 14c content. In another specific example, the acetic acid self-generating material used in the hydrogenation step It is formed by fermentation. The fermentation process is better by fermenting sugar into acetic acid by using an acetic acid production process or a homoacetogenic microorganism and producing very little, if any, carbon dioxide as a by-product. The carbon efficiency of the fermentation process is higher than that of the general process. A conventional yeast process having a carbon efficiency of about 67%, preferably greater than 7〇%, greater than 80〇/〇 or greater than 9〇%. Optionally, the microorganism used in the fermentation process is a genus ( Genus) is selected from the group consisting of cl〇stridium, Lactobacillus Uus, M〇〇rdla, Thermoanaerobacter, Propionibacterium (pr〇pi〇) Nibacter^um), Propionia spp. (Propionis Pera), the group consisting of anaerobic genus and acteriodes, and especially the species (printed as (2)) is selected from the group consisting of Clostridium formicoaceticum, Clostridium. Butyricum), Moorella thermoacetica, Thermoanaerobacter kivui, Bulgarian lactic acid bacteria (Lact〇bacillus delbrueckii), Propionibacterium acidipropionici, Propionispem arboris, A group consisting of Anaer〇bi〇spirmum succinicproducens, Bacteriodes amylophilus, and Bacteroides ruminicola, as appropriate, in this process, all or part of The unfermented residue of the self-generating material (e.g., woody substance) can be gasified to form hydrogen which can be used in the hydrogenation step of the present invention. An exemplary fermentation process for forming acetic acid is described in U.S. Patent No. 6,509,180 and in the United States. Publication Nos. 2008/0193 989 and 2009/0281354, the entire contents of each of which are hereby incorporated by reference. Limited to) agricultural waste, forest products, turf and other cellulosic materials, wood residues in wood yards, cork flakes, hardwood chips, branches, trunks, leaves f, bark 'sawdust, substandard pulp 'corn, corn sorghum, wheat Chips, rice crumbs, bagasse, switchgrass, miscanthus, animal waste, municipal waste, municipal sewage, commercial waste, grape pumice, apricot shell, large walnut shell, coconut shell, coffee break, grass, hay , wood grain, cardboard, paper, plastic and cloth. Other sources of biomass material are straw black liquor, which is an aqueous solution of lignin residues, hemicellulose, and inorganic chemicals. U.S. Reissue Patent No. RE 35,377 (a source for reference) provides for the manufacture of materials by converting carbonaceous materials such as oil, coal, natural gas and raw materials. Alcohol method: The system comprises hydrogenating a solid and/or liquid carbonaceous material to obtain a process disorder, which forms a joint with other natural gas vapors. The combined money is converted to methanol, which can be passed through the ship and the shaft acetic acid. The wealthy view of the line, to discuss the above-mentioned invention. U.S. Patent No. (1) discloses a process for converting waste biomass material into syngas via gasification, and U.S. Patent No. (10) 5,754 discloses a method for producing a hydrogen-containing gas nicotine wire. ^ ^ 虱 and feed into the weathering reaction of the stomach. Also includes its weaving _ and acid and B and C. Preferably, the suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, ethylene glycol, (iv), and acetic acid. Other compounds are also 201247300 which can be hydrogenated in the process of the invention. In some specific examples, the presence of a carboxylic acid such as propionic acid or its aldehyde may be advantageous in the manufacture of propanol. Water can also be present in the acetic acid feed. Alternatively, the acetic acid in the vapor state can be obtained directly from the crude product in a flash vessel of the decyl alcohol carbonylation unit as described in U.S. Patent No. 6,657,078, the entire disclosure of which is incorporated herein by reference. For example, the crude steam product can be fed directly into the ethanol synthesis reaction zone of the present invention without the need to condense or remove water from acetic acid and light sputum, thereby saving overall processing costs. The acetic acid may be vaporized at the reaction temperature, and then the vaporized acetic acid may be fed together with hydrogen in an undiluted state or hydrogen diluted with a relatively inert carrier such as nitrogen, argon, helium, carbon dioxide or the like. The reaction in the vapor phase of the system, the temperature, should be controlled so that helium does not fall below the dew point of the acetic acid. In one embodiment, acetic acid can be vaporized at a specific pressure at the boiling point of acetic acid, and then the vaporized acetic acid is further heated to the reactor inlet. In another embodiment, the acetic acid is mixed with other gases prior to vaporization, and then the mixed vapor rL is heated 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 of 125 C or below, and the combined gas stream is then heated to the reactor inlet temperature. Some specific examples of the process for hydrogenating acetic acid to form ethanol may include various configurations using a fixed bed reaction or a bed reactor. In many embodiments of the invention, a "insulation" reactor can be used, i.e., there is little or no need to pass an internal conduit into the reaction zone to add or remove heat. In other embodiments, a radial flow reactor (radialfl〇 can be utilized) Wreact〇r) or reactors, or a set of reactors in series, whether or not with or without heat exchange, quenching, or additional feed materials may be used. Alternatively, a shell with a heat transfer medium may be used. Tubular reactor. In many cases, the reaction zone can be housed in a single vessel or contained in a tandem vessel with heat exchange therebetween.. In a preferred embodiment, in a fixed bed reactor For example, a catalyst is used in a straight tube or tubular reactor where a generally vaporous reactant passes over or within the catalyst. Other reactors such as fluid or a volcanic bed reactor can be used. In some cases, the hydrogenation catalyst can be combined with an inert material to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant compound with the catalyst particles. The hydrogenation reaction can be carried out in the liquid phase or in the vapor phase. Preferably, the reaction is The column is carried out in the vapor phase at 201247300. The reaction temperature can range from 125 ° C to 350 ° C, such as from 200 ° C to 325 C, from 225 C to 300 C, or from 250 ° C to 300 ° C. It can be in the range of 1 kPa (kpa) to 3000 kPa, for example, from 50 kPa to 2300 kPa, or from 1 〇〇 kpa to 21 kPa. The reactants can be from 50 hours ^hr丨) to 50,000 hr-1 gas time and space. The velocity (GHSV) is fed into the reactor, such as from 5001^1 to 30,0001^1, from lOOOhr-1 to l〇, 000hr-i, or from 1000hr-i to 65001^1. Acetic acid consumes two moles of hydrogen to produce one mole of ethanol, but the actual molar ratio of hydrogen to acetic acid in the feed stream can vary from about 100:1 to 1:1, as from 5:1 To 1:50, from 20:1 to 1:2, or from 18:1 to 2:1. Contact or residence time can vary widely, depending on various variables, such as amount of acetic acid, catalyst, reactor, temperature And pressure. When using a catalyst system instead of a fixed bed, the general contact time is from a few milliseconds to more than a few hours, and at least the preferred contact time for the reduction is from 0.1 to 100 seconds. The alcohol is preferably carried out in the presence of a hydrogenation catalyst. Exemplary catalysts are described in U.S. Patent Nos. 7,6,8,744 and 7,863,489, and U.S. Patent Application Publication Nos. 2010/012m4 and 2010/0197985 For reference, in another embodiment, the catalyst includes a C〇M〇/S ship of the type described in U.S. Patent Application Publication No. 2〇〇9/〇〇696〇9. For some specific financial reasons, the catalyst may be a bulk catalyst. In one embodiment, the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, osmium, iridium, silver, ruthenium, titanium, ruthenium, ruthenium, ruthenium, and crane. group. Preferably, the first metal is selected from the group consisting of #, 纪, 26, and Guanlan. As mentioned, in some embodiments, the catalyst further comprises a second metal which generally functions as a promoter. If a second metal is present, it is preferably selected from the group consisting of copper, molybdenum, tin, lanthanum, iron, mm 钸, fierce, nail, ruthenium, gold, and gold. More preferably, the second metal is selected from the group consisting of copper, tin, tin, niobium and nickel. Where the catalyst comprises two or more metals, such as the first metal and the second metal, the first metal is present in the catalyst in an amount of 〇.a1〇wt%, such as self-driving. , or from 0.1 to 3 wt%. The second metal is preferably present in an amount of 〇 u2 〇 wt%, such as from 〇] to 12 201247300 10wto/〇 ’ or from 0.1 to 75 wt%. For example, the preferred metal domain of the heterozygous inclusion, your nail, such as chain n palladium / rhodium, cobalt / IS, cobalt / platinum 'start / network, Ming / nail ' # / tin, like, copper / handle, copper /word, record / Ji, Jin / Ji, 钌 / 铢, or 钌 / iron. The one catalyst may further include a third metal selected from any of the metals of the above-mentioned first metal wire, as long as the third metal is different from the first metal and the second metal. Preferably, the 'third metal is selected from the group consisting of secret, bismuth, bismuth 'copper, zinc, #, tin and antimony. When a third metal is present, the total amount of the third metal is preferably from 0.5 to 2 〇 wt 〇 /. , such as from 0.1 to l〇wt%, or from .1 to 7_5wt%. In a specific example, the catalyst may include a face, a tin, and a record. In addition to one or more metals, in some embodiments of the invention, the catalyst further includes a support or a modified support (m〇difled SUpp0rt). As used herein, the modified carrier „一四系 represents the carrier of the carrier material and the carrier modifier for adjusting the acidity of the carrier material. The total weight of the carrier or the modified carrier is the total amount of the catalyst. The weight is preferably from 75 to 99% by weight, such as from 78 to 95%, or from 80 to 975%. The preferred support comprises a ruthenium support such as ruthenium oxide, ruthenium oxide/alumina, ruthenium. a citrate such as calcium metasilicate, pyrolytic yttrium oxide, high purity cerium oxide and mixtures thereof. Other supports may include, but are not limited to, iron oxide, aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, carbon, Graphite, high surface area graphitized carbon, activated carbon and mixtures thereof. The support may be a modified support, and the amount of the support modifier present is from 1 to 50% by weight based on the total weight of the catalyst, such as self-twisting. Up to 25% by weight, from 1 to 2% by weight, from 3 to 15% by weight. In some specific examples, the carrier modifier may be an acid modifier that increases the acidity of the catalyst. Suitable acidic carrier modifiers are optional. Free Group IVB metal oxide, Group VB metal oxide, Group VIB metal oxide, νπΒ metal oxide, VmB metal oxide, aluminum oxide a group consisting of a mixture thereof. The acidic carrier modifier includes those selected from

Ti02, Zr02, Nb205, Ta205, Al2〇3, B2〇3, P2〇5, Sb203, W03, Mo〇3,

A group consisting of Pe2〇3 'O203 'V2〇5, Mn02, CiiO, C〇203, and Bi203. Preferred support modifiers include tungsten, turn and slave oxides. In another embodiment, the bulk modifier may be an alkaline modifier having low or no volatility. The alkaline modifier may, for example, be selected from (1) an alkaline earth metal oxide, (ii) an alkali metal c 13 201247300 oxide '(iii) a soil-measuring metal salt, (iv) a metal salt, ( v) Group of group IIb metal oxides '(vi) Iffi group metal metasilicate group metal oxides, (viii) mB group metal bismuth salts and mixtures thereof. The test carrier modifier may be selected from the group consisting of oxides and metasilicates of any of sodium, potassium, magnesium, calcium, strontium, barium, and zinc, and any of the foregoing oxides. In one embodiment, the alkaline modifier is calcium ruthenate such as cesium bismuth citrate (CaSiCb). Calcium metasilicate can be crystalline or amorphous (am〇rph〇us). The catalyst on the modified support may comprise one or more metals supported on the oxidized rock support, selected from the group consisting of platinum, palladium, cobalt, tin and antimony, and visible Optionally, the one or more modifiers are selected from the group consisting of bismuth decanoic acid and one of a plurality of oxides of tungsten, molybdenum and/or vanadium. The catalyst composition suitable for use in the present invention is preferably formed by metai impregnation in a modified support, but other processes such as chemical vapor deposition may be used. The aforementioned U.S. Patent Nos. 7,608,744 and 7, 863, 489, and U.S. Patent Application Publication No. 2, the entire disclosure of which is incorporated herein by reference. Catalyst. The reduction is in the state of the county, and there is a Tit line. The Gu New is continuously passed through the catalyst at an initial temperature of 4 。. In the specific case, the reduction is better at the catalyst loading. The hydrogenation reaction vessel is then carried out. In particular, the hydrogenation of acetic acid achieves an advantageous conversion of acetic acid and an advantageous selectivity for ethanol, yield. For the purposes of the present invention, the term "conversion" means conversion to acetic acid. The amount of acetic acid is converted. The conversion rate is expressed as a percentage of acetic acid in the feed. The conversion rate can be at least 4G%, such as at least, at least 6G%, at least muscle or at least ·. The rate of reading turtles is difficult, such as at least or at least 90%, but in some cases, a low conversion rate catalyst with high selectivity for ethanol is acceptable. The rate is based on the percentage of moles of converted acetic acid. It is understood that the self-acetic acid conversion/object has an independent selectivity and the selectivity and the conversion rate are also independent of each other. For example, it is better to convert the 6° mol% of the right-handed acetic acid into ethanol, and the ethanol conversion rate is _. The catalyst selectivity for ethanol is at least ·, such as at least ·, or at least _. Ammonia 14 201247300 The preferred embodiment of the process also has a low selectivity for the desired product, such as 曱 、, 乙 烧 = = carbon ° The selectivity of _ and other non-desired products is preferably less than 4%, such as less than 2% or / / "yield" is based on the specific product of hourly formation of gas enthalpy, such as ethanol The yield can be in the range of just up to 3, -g ethanol / public media / hour. ^ The specifics of the invention are as follows: the crude ethanol produced by the hydrogenation process, before any subsequent curing treatment such as purification and separation, Generally includes unreacted acetic acid, ethanol, and water. As described herein, nouns 'Cold ethanol product, which means any composition including from 5 to % of ethanol and from 5,4% by weight of water. The composition range for crude ethanol is shown in Table W. Hydrogen is excluded. "Others" may include, for example, vinegars, hydrazines, ketones, alkanes, and carbon dioxide. Table 1: Crude ethanol product composition component concentration (wt.%) concentration (wt·%) concentration (wt·%) Tang (Wt%, ethanol 5 to 72 15 to 70 15 to 50 25 to ^~ acetic acid 0 to 90 〇 to 50 0 to 35 〇 to 15 water 5 to 40 5 to 30 10 to 30 10 to 26 ethyl acetate 〇 to 30 1 to 25 3 to 20 5 to 18 acetaldehyde 0 to 10 0 to 3 0_1 to 3 0.2 to 2 Others 0.1 to 10 0.1 to 6 0.1 to 4 In a specific example, the crude ethanol product of Table 1 may have a low concentration of acetic acid. However, the conversion is high, and the acetic acid concentration may range from 0.1% by weight to 20% by weight, such as from 5% to 5% by weight, from 0.1% by weight to 10% by weight, or from 3% by weight to 5% by weight. In a specific example having a lower amount of acetic acid, the acetic acid conversion in the reactor is preferably greater than 75%, such as greater than 85% or greater than 90%. In addition, the selectivity to ethanol is also relatively high, and is preferably greater than 75%, such as greater than 85% or greater than 9 〇 0 / 〇. In one embodiment, the weight ratio of ethanol to water can be at least 〇18:1 or greater, such as at least 〇·5:ι or at least m. When expressed in terms of range, the weight ratio of ethanol to water can be from 18:1 to 5:1, such as from 0.5:1 to 3: or from 1:1 to 2: better than ethanol. Knowing the fermentation process, 15 201247300 Miscellaneous ethanol products have more ethanol than water... In the case of a newer case, a smaller amount of water may require less energy to remove ethanol and improve the overall efficiency of the process. Thus, in the female embodiment, the amount of ethanol in the crude ethanol product is from 15 wt% to 7 Gwt%, such as from 2 Gwt% to 7-% or from 25 passes to 7-%. Particularly preferred is a higher percentage by weight of ethanol. An ethanol recovery system according to an embodiment of the present invention is shown in Figure 7. Each hydrogenation system contains a suitable gasification reactor and a process for separating ethanol from the resulting crude ethanol mixture. System 100 includes a reaction zone 101 and a separation zone 1〇2. Figures 丨, 2, 4, 5 and 7 illustrate an exemplary system for recovering purified water as a co-product of the extractant. Figures 3 and 6 illustrate a system for recovering a dilute acid stream as an extractant. As shown in Figures 1-7, the reaction zone 1〇丨 includes a reactor 1〇3, a hydrogen feed line 1〇4, and an acetic acid feed line 105. Hydrogen and acetic acid are fed to the vaporizer u〇 via lines 1〇4 and 1〇5, respectively, and a steam feed stream is produced in line 111, which is introduced into reactor 1〇3. The feed to reactor 103 includes fresh acetic acid. In one embodiment, lines 1〇4 and 1〇5 can be combined and combined into a vaporizer 110, such as with a stream containing both hydrogen and acetic acid. The steam feed stream temperature in line 1U is preferably from 10 ° C to 350 ° C, such as from 120 ° C to 310 ° C or from 150 ° C to 300 ° C. Any feed that has not been vaporized is removed from the vaporizer 110 via a discharge pipe (bl〇wd〇wn) n〇. Further, although line 111 is shown as being introduced into the top end of reactor 1〇3, line 111 can be introduced into the side, upper or bottom of the reactor. Reactor 103 contains a catalyst for hydrogenating the acid, preferably a catalyst for hydrogenating acetic acid. In one embodiment, one or more guard beds (not shown) may be used upstream of the reactor 103 (as may be upstream of the vaporizer 11) to protect the catalyst from contact or return/circulation. Poisons contained in the stream or impurities that are not expected. This guard bed can be used in a vapor or liquid stream. Suitable protective bed materials may include, for example, carbon 'oxide oxide, oxidized, ceramic or resin. In one such state, the guard bed media is functionalized, such as functionalized with silver, to capture a particular species such as sulfur or halogen. In the hydrogenation process, the crude ethanol product is withdrawn (preferably continuously withdrawn) from reactor 103 via line 112. The crude ethanol product in line 112 can be condensed and fed to separator 1〇6, which in turn k is supplied to vapor stream 114 and liquid stream 113. The separator 106 can, for example, include one or more flash 5| or a knockout pot. The separator 106 can be operated at a temperature from 20 ° C to 350 ° C, such as from 3 CTC to 201247300 325 ° C or from 60 ° C to 250 ° C. The pressure of the separator 106 can range from 1 kPa to 3000 kPa', such as from 125 kPa to 25 Torr OkPa or from isokPa to 22 kPa. Optionally, the crude ethanol product in line 112 can be passed through one or more membranes to separate hydrogen and/or other non-condensable gases. The vapor stream 114 from the separator 106 can include hydrogen and hydrocarbons and can be purged and/or returned to the reaction zone 101. As shown, the vapor stream 114 is combined with the hydrogen feed 1〇4 and co-fed into the vaporizer 110. In some embodiments, the returned vapor stream 114 can be compressed prior to being combined with the hydrogen feed 104. The liquid stream 113 from the separator 106 can be withdrawn and pumped into a first column 1 〇 7, also referred to as an "extraction column". The liquid stream 113 can be heated from ambient temperature up to 70 ° C, such as up to 5 Torr. 〇 or at most 40. (: The liquid stream 113 is preheated to above 7 〇. (: The additional energy required in the first column 107 relative to the reboiler duty cannot achieve the desired energy efficiency. In the example, the liquid stream 113 is not preheated, but is below 7 〇. 〇, such as less than 50. (: or below 40C, it is extracted from the separator no and fed directly into the first column 1〇 7. In one embodiment, the contents of liquid stream 113 are substantially similar to the crude ethanol product obtained from the reactor, but hydrogen, carbon dioxide, methane, and/or ethane have been removed from the composition. Preferably, the liquid stream 113 can also be referred to as a crude ethanol product. The exemplary composition of the liquid stream 113 is shown in Table 2. It should be understood that the liquid stream 113 can contain unlisted Other components in 2. 17 201247300 Table 2: Feed composition for column 107 (liquid stream 113) Concentration (wt.%) Concentration (Wt.°/〇) Degree of attack (Wt.0/o) Ethanol 5 to 72 10 to 70 15 to 65 Acetic acid <90 5 to 80 to 35 water 5 to 40 5 to 30 10 to 26 ethyl acetate <30 1 to 25 3 to 20 acetaldehyde <10 0.001 to 3 〇.1 to 3 acetal <5 0.01 to 5 〇.〇1 to 3 丙_ <5 0.0005 to 0.05 〇·〇01 to 0.03 In the table of the entire specification, less than ( The amount indicated by <) is preferably absent or, if present, greater than 0.001 wt%. In one embodiment, the concentration of ethyl acetate in liquid stream 113 can affect the load and size of the first column. Reducing the ethyl acetate concentration reduces the reboiler load and size. In a specific example, in order to reduce the ethyl acetate concentration, the catalyst in the (a) reactor is converted to acetic acid in addition to the conversion of acetic acid; (b) the catalyst is less selective to ethyl acetate, and / Or (c) the feed to the reactor (including the recycle) may contain less ethyl acetate. As shown in the figure, the liquid stream 113 is introduced into the upper portion of the first column 107, such as a portion of 1/2 height or 3/2 如上 as above. As shown, one or more extractants 115 are also introduced into column 1〇7 as described above to assist in separating the ethanol from water (and other components). Preferably, the extractant is recovered directly or indirectly from the first residue and recycled back to the first column 107. As shown, a fresh extractant, indicated at 125, may also be added as appropriate. The extractant 115 is preferably introduced above the liquid stream 113. Preferably, the extractant is introduced adjacent to the upper portion of the column and flows downward until it reaches the reboiler. The extractant 115 is preferably introduced at a point above the feed point of the liquid stream 113. In some embodiments, the extractant 115 can be heated from ambient temperature up to 7 (rc, such as up to 5 Torr. or at most 40 ° C. Another specific example, the extraction 扉 5 wire is additionally preheated, but as Figures 1 through 7 are not taken from other towers and, if necessary, cooled to less than 7 〇. 〇, such as below 5 〇 it or below 40 ° C, and fed directly into the first tower 1 〇 7 As shown in Figure 6, depending on the ethyl acetate concentration of the ethyl acetate recycle stream 147, this stream is introduced above or below the feed point of the liquid stream 113 201247300. The extractant 115 is preferred. The feed point is higher than the feed point of the ethyl acetate recycle stream 147. Depending on the target value of the ethyl acetate concentration in the first column 1〇7 distillate, the feed point of the ethyl acetate recycle stream 147 will be The extractant 115 preferably comprises water that has been flowed into the system. As described herein, the extractant 115 can be obtained from a portion of the second residue. The extractant 115 can comprise up to 2% by weight of acetic acid. For example, at most 10 wt% of acetic acid or a dilute acid stream of up to 5 wt% acetic acid. In one embodiment, the mass flow ratio of water in the extractant 115 is for liquid The mass flow ratio of the stream 113 may be from 0.05:1 to 2: such as from 0.07 to 0.9:1 or from 0.1:1 to 〇.7:1. Preferably, the mass flow ratio of the extractant us is smaller than that of the liquid stream 113. Mass flow ratio. In the specific example, the first column 107 is a plate column having a theoretical plate number of 5 to 90, such as from 10 to 60 theoretical plates or from 15 to 50 theoretical plates. Depending on the efficiency of the panel, the efficiency of the panel will typically be from 0.5 to 〇7 depending on the type of panel. The panel may be a screen, a fixed valve plate, a movable valve plate or any other suitable design known in the art. For example, a packed column with structured packing or random packing can be used. When the first column 107 is operated at 50 kPa, the temperature of the residue flowing out of the line 116 is preferably from 20 ° C to 10 ° C, such as From 30. (: to 90. (: or from 401 to 80. (:. Tower 107 substrate is mainly maintained at a relatively low temperature by extracting a liquid stream comprising ethanol, ethyl acetate, water and acetic acid, thus providing energy efficiency Advantages: The temperature of the outlet from the tower 117 from the tower 117 is preferably from 50 kPa to 10 ° C to 80 ° C, such as from 20 ° C to 70. (: From 30 eC to 60 ° C. The pressure of the first column 107 can range from 0.1 kPa to 510 kPa 'from ikpa to 475 kPa or from 1 kPa to 375 kPa. In some specific examples, the first column 1 〇 7 can be below 7 〇 kPa, operating in a vacuum below 5 〇 kpa or below 20 kPa. Operating in a vacuum reduces the reboiler load and the reflux ratio of the first column 1 〇 7 . However, reducing the first tower 1 〇 7 The operating pressure does not substantially affect the column diameter. The extraction dose fed to the extraction column 107 can vary widely. For example, when the extractant U5 includes dilute acid water, the mass flow ratio of water to the crude ethanol product can be 5:1. To 2: Bu Ruo 7 to 0, 09:1 or from 0. U to 0.7:1. The crude ethanol product in liquid stream 113 includes ethyl acetate, ethanol, and water. These compounds form a binary azeotrope and a ternary azeotrope. For example, the ternary azeotrope may have a lower boiling point than its constituents, while other ternary azeotropes may have a boiling point of 201247300 between the pure constituents. In a particular embodiment of the invention, a greater proportion of ethanol will be carried into the first distillate in line 117 when no extractant is used. By using the extractant in the first column 101, it accelerates the separation of the ethanol to the first residue in line 106, thereby increasing the overall yield of the ethanol product in the first residue in line 116. In this manner, ethanol, water, unreacted acetic acid, and other heavies are removed from liquid stream 113, and the wound, if present, is withdrawn as the first residue in line 116 (preferably continuously withdrawn) ). The first column 107 also forms a first distillate which is pumped out of line 117 and which may be condensed and in a ratio of, for example, 30:1 to 1:30, such as from 10:1 to 1:1 or from 5: A ratio of 1 to 1:5 is refluxed. The higher mass flow ratio of water to organics allows the first column i 〇7 to operate at a reduced ratio. The first crane product in line 117 preferably includes the majority of the weight from liquid stream 113 = and ethyl acetate. - In a specific example, the first take-up in the line m includes the acetic acid acetabulum: (1) in the acetic acid, and the water thorn (10) B, and more preferably less than ^ specific examples t The first - in the line m also includes ethanol. Ethanol is returned to increase the ethanol efficiency of the ruthenium capacity. In order to return, the material can be fed to an extraction column (not shown) to recover the ethanol and reduce the ethanol concentration of the reactor to the reactor 1〇3. The composition of n1G7, the output and the composition of the residue. And the domain _ _ and _ _ village containing silk clock with the score of the table = =,, s, = tower of the goods and residues are also known as, the first museum,, or, first The exhibits or residues of the disabled 1#fr^ may also be referred to as similar numbering modifications (eg, second, peaks distinguishing such 'but this modification should not be interpreted as requiring any particular cis 20 201247300 Table 3: Extraction Tower L〇7 ------ Concentration (wt.0/〇) Concentration iwt.0/〇) 罘一 distillate ~ G alcohol water <25 0.001 to 20 0.01 to 15 〇·1 to 20 1 to 15 2 to 10 acetic acid <2 <0.1 <0.05 ethyl acetate 10 to 85 15 to 80 20 to 75 junacet acetal 0·1 to 70 0.2 to 65 0.5 to 65 <3 0.01 to 2 〇.〇5 to 1.5 First residue acetic acid water 7 3C^r 0.1 to 50 0.5 to 40 1 to 30 20 to 85 25 to 80 30 to 75 Ck alcohol 1 to 75 15 to 70 20 To 65 esters 0.005 to 30 0.03 to 25 0.08 to 1 In a specific embodiment of the invention, the first column 107 can be removed in most of the water, ethanol and acetic acid - the residue stream and only a small amount of ethanol and water are collected to the German Operating at the temperature of the liquid stream, t is due to the formation of a binary azeotrope and a ternary azeotrope. The weight of water in the residue in line 118 may be greater than 1:1, such as greater than 2:1, by weight of water in the distillate in line 119. The weight ratio of ethanol to ethanol in the residue may be greater than 1:1, such as greater than 2:1. The amount of acetic acid in the first residue can be mainly determined depending on the conversion rate of the reactor 1〇3. A specific amount of acetic acid in the first residue is less than 1 Gwt% '& - Specific Example t, when the conversion rate is low, for example less than 90%, the amount of the first residue + acetic acid may be greater than the wrist %. The water in the residue contains both the water present in the crude ethanol product produced by the hydrogenation of the counter-filament and the water fed to the column 1〇7 as the extractant m. When it is added as an extract, the amount of water in the residue will increase by 4%, the amount of money will increase, and the amount of water will be reduced in the first residue. For example, the ethyl acetate in the first residue may be extremely low in the range of iwppm to 800wppm and more preferably. Preferably, the first German product in line 117 is substantially free of acetic acid, for example comprising less than 21 201247300 lOOOwppm, less than 500 wppm or less than 100 wppm acetic acid. The distillate can be scrubbed from the system or recycled, in whole or in part, to reactor 1〇3. In some embodiments, when the distillate/ethyl acetate and acetaldehyde are included, the distillate may be further converted into an acetaldehyde stream and an ethyl acetate stream, for example, in a distillation column (not shown). The ethyl acetate stream can also be hydrolyzed or hydrogenolyzed to produce ethanol. One of the streams can be returned to reactor 1〇3 or separated from system 100 as a foreign object. Some species, such as acetals, can be decomposed in the first column, so that there is very little or even no measurement of the distillate in the distillate or residue. Further, an equilibrium reaction between acetic acid/ethanol and ethyl acetate may occur after the crude ethanol product has flowed out of the reactor 103. Depending on the concentration of acetic acid in the crude ethanol product, this equilibrium can be driven to the formation of ethyl acetate. This reaction can be adjusted via residence time and/or crude ethanol product temperature. - In a specific example, the balance is favored by acetification to produce acetic acid due to the composition of the first residue in the line 117. Although the g is capable of consuming ethanol in the liquid or gas phase, the hydration can also reduce the amount of acetic acid that must be removed by the process. Ethyl acetate can be transferred from the first column 1 = 7 = via the first column 1G7 and the second column 旨 旨 旨 就 就 。 。 。 。 。 The brewing can be accelerated by passing a portion of the residue of the line 118 to the reactor (not shown). The esterification reactor can be a liquid or vapor phase reactor and can include an acidic catalyst. Preferably, a vapor phase reactor is preferred for converting some of the first residue to an intermediate vapor feed to be introduced into the second column 1-8. ° As shown in Fig. 1, in order to recover ethanol, the first residue 116 may be further separated depending on the concentration of acetic acid and/or ethyl acetate. In most embodiments of the invention, the residue stream iΜ is introduced into the second column 1 8 (also referred to as the "acid column") because any acid from the first residue 116 is removed. In the second tower 108. When the concentration of acetic acid in the first residue is more than 1% by weight, such as more than 5% by weight, an acid separation column can be used. In some specific examples, when the acid concentration is low, such as less than 10% by weight, the water separation column in Figure 3 can be used. In Fig. 1, the first residue in line 116 is introduced into second column 1 8 , preferably to the upper half or upper 1/3 of the upper portion of column 108. The second column 1 8 produces a line enthalpy; the second residue comprising acetic acid and water, and the second column comprising ethanol in line 119. 22 201247300 In one embodiment, the majority of the weight of water and/or acetic acid fed to the second column 108 is removed to a second residue in line 118, such as at least 6% water and/or acetic acid removed. The second residue towel in the pipeline is 'or better than at least 8Q% water and/or acetic acid is removed. For example, when the concentration of acetic acid in the first residue is greater than 5 〇 wppm, such as greater than 0.1% by weight, greater than 1% by weight, such as greater than 5% by weight, an acid column may be desirable. In a specific example, the first residue in the line 116 can be preheated before the second column 1 8 to pre-heat the second residue in the line 116 to be the residue of the second column 1 or the second column 1 〇 8 of the top steam - heating. In some specific embodiments, if acetic acid is present, the acetification can be carried out in a vapor phase (not shown) which results in partial preheating of some of the first residue in the tube and line 116 to form a secondary steam feed. For purposes of the present invention, when preheating, it is preferred that less than 30 mole percent of the first residue in the stream ι is a vapor phase, such as less, less than 25 mole percent, or less than 20 mole percent. The more vapor phase content results in an increase in energy consumption and results in a significant increase in the size of the second column 1〇8. The acetateization in the first residue in line 116 increases the concentration of ethyl acetate which results in an increase in the size of second column 108 and an increase in reboiler loading. Thus, acetic acid conversion can be controlled based on the initial ethyl acetate concentration from the first column. In order to maintain effective separation, the concentration of ethyl acetate in the first residue fed to line 116 of the second column is preferably less than, for example, less than 800 wppm or less than 600 wppm. The second column 108 is operated in a manner that concentrates the ethanol from the first residue such that most of the ethanol is carried to the top of the column. Thus, the residue of the second column (10) may have a low ethanol concentration of less than 5% by weight, such as less than 1% by weight or less than 5% by weight. Lower ethanol concentrations can be achieved without significantly increasing the recombiner load or column size. • Some have a towel to effectively reduce the concentration of ethanol in the residue to less than 50 κρρπι, or more preferably less than 25 wppm. As described herein, the residue of the second column 108 can be treated and the lower concentration of ethanol allows the residue to be treated to produce other impurities. Although the temperature and pressure of the second column 1 8 may vary, the temperature of the second residue in the line (10) is preferably from 95 when at atmospheric pressure. (: to 160. (;:, as from 1〇〇. (: to 15〇. (: or from 110 ° c to 145 ° c. - specific wealth, when the tube of the 6th towel - residual _ preheated to The temperature at the second residue of the line 118 is 2〇. (: the temperature inside, such as within 15 〇 or 1 〇 1 to 23 201247300 from the second tower 8) The Γ Γ can be bribe or thief to blow. In the second coffee war temperature ladder - tower 108 pressure can be from 0 to 510 coffee g, for example, from running to 47 her or from lkPa to 375kPa Scope... In a specific example, the second gamma 8 system is operated above atmospheric pressure, such as above 170 kPa or above 375 kPa. The second tower 1 8 may be composed of, for example, M6LSS, 11〇丨2205 or also 11 (^ material) Depending on the operating pressure, the reboiler load and column size for the second column can be maintained constant until the second ethanol concentration in line 119 is greater than 90% by weight. As described herein, the first column 107 is preferably used. An extraction column of dilute acid stream. The additional water system is separated in the second column 108. Although the use of a dilute acid stream as an extractant can reduce the reboiler loading of the first column 1〇7, when the water is organic If the mass flow ratio of the liquid stream 113 is greater than 0.65:1 'if greater than 0.6:1 or greater than 0.54:1, the additional dilute acid stream will cause an increase in the reboiler load of the second column 1〇8, which will be offset by Any benefit obtained by a column 107. The second column 108 also forms an overhead which is drawn in line 119 and which can be condensed and, for example, from 12:1 to 1:12, such as from 10:1 to 1:1. Or refluxing from a ratio of 8:1 to 1:8. The overhead in line 119 preferably comprises from 85 to 92 wt% ethanol, such as from about 87 to 90 wt% ethanol, with the balance being water and ethyl acetate. An exemplary composition of the German and the residue composition is shown in Table 4 below. It should be understood that the distillate and residue may also contain other components not listed in Table 4. 24 201247300 Table 4: Concentration (wt.%) Acid Tower 108 (Fig. 1) Concentration (wt.%) Concentration (wt%, second distillate ethanol ethyl acetate acetaldehyde water 70 to 99.9 <10 <5 0.1 to 30 75 to 98 0.001 to 5 0.001 to 1 1 to 25 80 to 95 0.01 to 3 0.005 to 0.5 5 to 20 Second residue acetic acid water ethyl acetate ethanol 0.1 to 45 45 to 100 <2 <5 0.2 to 40 55 to 99.8 <1 0·001 to 5 0.5 to 35 65 to .99.5 <0.5 <2 b Line 119 The ethanol in the second distillate is 1 by weight and at least 35:1 by weight of ethanol in the second residue in line 118. In one embodiment, the weight ratio of water in the second residue to water in the second effluent 119 is greater than 2:1, such as greater than 4:1 or greater than 6:1. In addition, the weight of acetic acid in the second column of the product 118 is better than the weight of the acetic acid of the second residue 119, such as greater than 15:1 or greater than 2 〇: the second remaining product in the better pipeline (10) is substantially not Contains acetic acid and may contain traces of acetic acid (if _). The reduced acetic acid concentration of the line (10) towel advantageously provides an ethanol product which is also free of acetic acid or traces of acetic acid. Preferably, the #朗9 towel takes care of the second, and is substantially free of acetic acid (four). The second crane product in line 119 can be withdrawn as an ethanol product or processed to a reduced water concentration. In the figure 1, in order to recover water as the extractant for the first column 107, the first-residue in the line 118 is separated into a liquid-liquid acetic acid liquid stream. The column is attached to the second precursor of the separation line 1 and is fine. The other fraction 2, molecular sieve or membrane as shown in the fourth step can be used to separate the second residue in _18. The second residue in the official line is guided into the third tower 1G9, preferably above the upper portion of the tower 1G9, as in the above portion. Preferably, the first collapse of the fine 21 comprises water and a small amount of acetic acid such as f or less than 1 wt% e. Even though the third take-up in the line 121 includes less I B, it may still be a suitable acid to be extracted. In stream (2) 25 201247300 distillate may be returned to first column 107 as extractant 115 or may be purged if desired. Third column 109 may be a plate column or packed column. In one embodiment, the third column 109 can be a plate column having a number of plates of 5 to 150, such as from 15 to 5 plates or from 2 to 45 plates. Although the temperature and pressure of the third column 109 may vary, the temperature of the third residue flowing out of the line 12 is preferably at 115 when at atmospheric pressure. (: to 14 〇. (:, such as from 丨 to 丨 ^ it or from 125 7 to 135 ° C. The temperature of the third distillate leaving line 121 is preferably 9 大 at atmospheric pressure. <t to 110C, such as from 95 ° C to 11 (TC or from loot to 11 〇. (: The pressure of the third tower 1 〇 9 can be from O.lkP to 51GkPa ' as from ikpa to ^kPa or from lkPa In another specific example, the acid column liquid can be operated by extracting a second residue comprising acetic acid and a second distillate comprising ethanol and water. The water is recovered by separating ethanol and water. 2, the second tower 122 may be a plate tower or a packed tower. "In the specific example, the second tower 122 has a number of f 5 to 70 plates, such as from 15 to 50 plates or from 20 to 45 plates. The slab tower. When the column 122 is operated at a quasi-atmospheric pressure, the temperature of the residue flowing out of the line 123 is preferably from 95 〇 to 13 〇 ° C, as from or from 11 (rCi 115t: from the tower 122 In line 124, the temperature of the output is preferably from 7〇〇c to jj, such as from 751 to 951 or from the appearance to 9〇C. In other specific examples, the pressure of the second column 122 can be from 〇lkp to 5l〇kpa, such as from 475kPa or from 咖 to 375 must be. The second tower 122 library and residue examples of components are shown in Table 5. 26 201247300 Table 5: acid tower 122 (2nd Figure) Concentration (wt· %); Nongguang iwt%) Concentration (Wt.%) Crane product Ethanol 10 to 85 15 to 85 20 to 85 Water 5 to 60 10 to 50 10 to 45 Acetic acid < 2 0.001 to 0.5 〇.〇1 to 0.2 ethyl acetate <0.5 <0.01 0.001 to 0.01 acetaldehyde <2 <0.01 0.001 to 0.01 residue acetic acid 60 to 1〇〇 65 to 100 85 to 95 water <30 0.5 to 30 1 to 15 ethanol <1 <0.9 <0.07 The second residue in line 123 can be recycled to reaction zone 101. In some embodiments, the water in the second residue, if present, can be recovered and used as an extractant. In some specific examples, when the acetic acid concentration is 咼, such as 60 to 100%, if the residue is used as a dilute acid stream, water may be added to dilute the acetic acid. In other embodiments, when the residue comprises a very small amount of acetic acid, such as less than 5 wt% or less than 1 wt〇/〇, the residue may be neutralized and/or diluted prior to disposal in a wastewater treatment plant. The organic content of the residue, such as the acetic acid content, may be advantageously suitable for feeding microorganisms in a wastewater treatment plant. As shown in Figure 2, the remaining water from the second library in line 124, if any, is removed in other embodiments of the invention. Depending on the water concentration, the ethanol product may be derived from the second German product in ϊ124. In some applications, such as the use of ethanol in the health industry, the water in the ethanol product is tolerated, while other _ _ _ _ can use several different separation techniques from the pipeline to the second including the use of distillation towers, membranes, adsorption units And their combinations. "Technology - specific shot, the object can be called after the water is removed. The second museum's output is fed into the third column 126, such as the ethanol product grade ', the third distillate in the fines (ethanol distillation) The third residue in the line 127 or one of its residues (water residue J is returned to the first column 107 as 27 201247300 extractant. It is required as an extractant) Depending on the amount of water, a portion of the third residue in line 127 may also be purged. The second distillate in line 124 may be directed to the lower end portion of column 126, at the lower half or at the lower third. The output 128 is preferably refluxed at a reflux ratio of, for example, 1:1 Torr to 10:1, such as from 1:3 to 3:1 or from 1:2 to 2: 1. The third column 126 is preferably as described above. The plate column is preferably operated at atmospheric pressure. The temperature of the third distillate flowing out of the third column 126 is from 60 ° C to ihtc, such as from self-contained to c c. When the column is operated at atmospheric pressure, the third residue temperature in line 127 is preferably from 70. (: to 115. (:, from 8 ° C to 110 ° 〇 or from 105 to C ° C. Three towers 126's care and disability An exemplary composition of the composition of the composition is shown in Table 6. The extracts and noodles may also contain other components not listed, such as the components in the feed. Table 6: Ethanol product column 126 concentration (wt%) Concentration (wt.%) Concentration (wt·%) Distillate ethanol 75 to 96 80 to 96 85 to 96 water <12 1 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 75 to 1〇〇 80 to 100 90 to 100 Ethanol <0.8 0.001 J. 0.5 0.005 to 0.05 ethyl acetate acetic acid <1 0.001 to 0.5 0.005 3- 0.2 <2 - 0.001 to 0.5 0.005 to 0.2 In another specific example, it is preferred that when the acid conversion rate is higher in the reactor 103, the column can be used to recover the ethanol product and the water as the extractant. . In Figure 3, the first residue in line 116 is fed into second column 129, which is referred to as the "dilute acid recovery column". The second = 129 in Figure 3 can be similar to the first The second column operates to remove most of the water from the residue. The water from the line 116 can be separated into the second residue of the line 132 and returned to the first column. There may be some acetic acid in the second residue in line m (also referred to as 28 201247300 as a dilute acid stream) and the scrubbing 133 may be withdrawn if desired. In some embodiments, the dilute acid stream 132 may comprise at least 85 from the crude ethanol product II3. % acetic acid, such as at least 90 〇 /. and more preferably at least 99%. When expressed in ranges, the dilute acid stream includes from 85% to 99.5% or from 90% to 99.99% unreacted from the crude ethanol product. In some embodiments, the dilute acid stream comprises from 2 to 60 wt% acetic acid and from 40 to 98 wt% water. In one embodiment, the second residue in line 132 can be returned to the first column 1〇7, even It contains acetic acid. For example, the dilute acid stream may contain less than 30 wt%, such as less than i5 wt%, less than l wt%, or less than 5 wt% of B. Acid. When a higher concentration of acetic acid is present in the second residue 132, a water separator can be used to separate the water and acetic acid. For example, an adsorption unit, membrane, distillation column, other suitable water/acid separator, or a combination thereof. The pressure swing adsorption unit Qjressure swing ads〇rpti〇n unit) removes water from acetic acid. An acid resistant water permeable membrane can be used. In Fig. 4, the first residue in the line 116 is fed in a similar manner. The second column operated in the second column 134 of Figure 1. The water and acid from the first residue in line 116 can be separated into a second residue in line 136 and fed into water separator 138. Water separator 138 The second residue 116 is separated into a water stream in line 139 and an acetic acid stream in line 140. In some embodiments, the water stream may include a small amount of acetic acid and may be referred to as a dilute acid stream. Less than 30% by weight, such as less than 15% by weight, less than 1% by weight or less than 5% by weight of acetic acid. Depending on the amount of acid in the second residue 136, in some specific examples, the second residue It can be removed in 37% of the line ,, recycled in the reaction zone 1〇1 or treated as described above. As shown in Fig. 4, the aqueous stream 139 can be returned as an extractant to the first column 107. There is some acetic acid in the water stream of 139%. In one embodiment, the aqueous stream 39 is returned to the first column 107 before returning to the first column 107. It can be combined with fresh water. The acetic acid stream 14 from the water separator 138 preferably contains a high concentration of acetic acid. The acetic acid stream 14 〇 can be returned to the reactor zone. In a specific example, the second residue from the acetic acid column The acetic acid in the liquid stream can be reacted to leave a stream of purified water. In Figure 5, the second residue 132 is introduced into the third column 141 for esterification. In a specific example, substantially all of the unreacted acetic acid is reacted in the second residue Π2. The methyl acetate present in the second residue 132 according to the present invention reacts with the methanol stream in the line 142 in the esterification unit 141 to produce methyl acetate in the line 143. Although it is shown to react with sterols, it should be understood that other alcohols may be used which comprise a mixture of ethanol or alcohol. 29 201247300 For example, if ethanol is used instead of decyl alcohol, ethyl acetate is produced in line 143. As shown in Fig. 5, the esterification unit is shown as a reaction vaporization column (third column) 141. The second residue 132 is fed together with the methanol stream 142 into the third column 141 to produce a third distillate stream 143 comprising methyl acetate and a third residue stream 144 comprising water. Figure 5 shows the methanol feed stream 142 fed to the third column 141 at a lower point than the second residue feed column. In other embodiments, the sterol feed stream can be fed to the third column 141 to the same extent or fed below where the second residue 132 is fed. When the third column 141 is a reactive distillation column, as shown in Fig. 5, the third column 141 includes an ion exchange bed, an acidic catalyst, or a combination thereof. Non-limiting examples of ion exchange resins suitable for use in the present invention include macroporous strong acid cation exchange resins such as by Dow Chemical Company (D〇w

Amberiyst® series (such as Amberlyst 15®, approved by the Chemical Company)

Amberlyst35®, and Ambeirlyst36®). Other ion exchange resins suitable for use in the present invention are disclosed in U.S. Patent Nos. 4,615,806, 5,139, 981, and 7, 588, 690, the entire disclosures of In other specific examples, an acid is added to the third column to catalyze the esterification reaction. In this aspect, the acid may be selected from the group consisting of sulfuric acid, dish acid, acid, hetero 〇p〇lyacids, other inorganic acids, and combinations thereof. In another specific example, the acid catalyst comprises zeolite and a support treated with a mineral acid and a heteropolymer. In some specific examples, when an ion exchange resin is present in the third column 141, the second residue m can be fed into the guard bed before being fed into the second tower (4) (not shown in a specific example, the guard bed includes ion money fine The above, if not limited by the special theory, the guard bed removes one or more kinds of ship metals present in the second residue 132, thereby making the ion exchange resin present in the third column 141 Any deactivation of the catalytic position of the exchange resin is minimized. The (iv) parameter of the third column 141 may change the desired composition of the third stream 143 and/or the residue stream I44. For example, some specific examples The temperature 'grinding, feed rate and residence time can be varied to increase the conversion of acetic acid to the desired conversion, reduce the formation of impurities, achieve more efficient separation, reduce energy consumption, or a combination thereof. In a specific example, The three towers 141 are from 10 〇. (: to 15 〇. 〇, such as from 1〇〇π to 130C or from 100 (: to 12() (: base temperature operation. When reading force, reactive steaming 30 201247300 Guta can be pressed at atmospheric pressure, subatmospheric pressure or super-domain For example, in some cases, the anti-hybrid steam tower is in the range of 5 〇 to 5 ,, such as the operation of the copper running ❹ 50kPa to 200kPa. 1:1 to 1:2 In one example, the feed rate of acetic acid and alcohol fed to the third column (4) can be adjusted to control the molar ratio of acetic acid to alcohol fed to the third column (4). For example, some specific amounts of acetic acid fed to the reaction The molar ratio of sterol is from 1:1 to 1:15, such as the retention time of methane from the m.5 third tower. Some specific wealth, for example, the residence time in the second tower is self-existing. Hours, such as 3 hours or less than 1 hour from 1 JL. The third library output in the line 141 flowing out of the third column 141 preferably comprises at least iSwt% acetic acid vinegar 'better at least 35 wt% methyl acetate, or better at least 65 pain acetic acid methyl vinegar. When expressed in terms of range, the third material from the third column 141 may include a self-contained sensation, such as from 0 to 90% by weight or from 50% to 9% by weight. When the acetic acid is reacted, some sterol may be present in the third analog 143. Therefore, the third crane product (4) may include from ο] to 8 Gwt%, such as from 10 to 60 wt% or Amount of sterol from 1 to 30 wt〇/〇. Some impurities such as dimethyl ether may also be formed in the tower (10) during the reaction. These impurities may be present in a very small amount or even in a quantity. In some cases, the third museum's U3 includes less than 100 plus 3%, such as less than 75 〇qing or less than 500wppm. $5 in the 'Second Hall's effluent 143 The reactor can be fed to the reactor for the production of acetic acid, which can then be used as a feed for the ethanol synthesis reaction. In some embodiments, the third residue stream I43 can be condensed and treated before being fed into the reactor. Or a purification. A specific example of the towel 'Because the first reading 13 wipes the purpose of the B, the additional third column 146 can be used. A third column 146 (also referred to as "light hydrocarbon, column) is used to remove the acetic acid from the second column (3) and produce an ethanol product in the third residue in line 148. The light smoke tower 146 can be a plate tower or a packed tower. The n-stage 146 of Fig. 6 can be a plate column having a number of 5 to 9 theoretical plates, such as from 10 to 60 theoretical plates or from 15 to 50 theoretical plates. The feed position of the second feed 131 can vary with the ethyl acetate concentration and the ethanol 31 201247300 mixture stream 131 is preferably fed to the upper portion of the third column 146. The higher concentration of acetic acid is from the higher position of the column 146. The feed position should be avoided at the upper upper plate, close to the reflux, and the need for the reboiler load on the column and increase the column size. For example, in a tower with a number of plates, the feed position should be between the first and the 15th from the top. The feed at this point may increase the reboiler load and the size of the light hydrocarbon column. s. In the second museum, the outlet 131 can be at most 7 (TC, such as at most 50. 〇 or at most 4 〇. The third column 146. In some specific examples, there is no need to further the second residue. The concentrate can be concentrated in a third feed in line 147. The feedstock in line 147 also includes substantial mass of ethanol due to the relatively low amount of ethyl acetate fed to third column 146. In order to recover the ethanol, the third column in the line 142 can be fed into the first column as the ethyl acetate circulating liquid stream 147. Since this increases the demand for the first column and the second technique, it is better in the line 147. The ethanol concentration of the three-shop towel is from 7〇 to ^ from 72 to 88wt% ' or from 75 to 85wt%. In other specific examples, part of the third library in line 147 can be used as an additional product such as ethyl acetate. The solvent is removed from the system. In the specific case, the third residue may be further processed to recover ethanol having the required amount of water, for example, other fine columns, adsorption units, membranes or cylinders may be used if necessary. And the step-by-step removal of the third residue from the line 148 in most of the specific examples, using The separator removes the water prior to the third column 146 and thus does not require the stepwise drying of the ethanol. The second column 146 of the knives is preferably a plate column as described above and preferably operates at atmospheric pressure. The temperature of the third residue in line 148 flowing out of 146 is preferably self-staining to 1 io °c, such as from 7 (rc to ioo °c or from 80 to 〇. 管线. line flowing from third column 146 The temperature of the second distillate in 147 is preferably from 3 〇. (: to 7 〇. (:, such as from 4 〇 it to 65 50 ° C to 65 ° 〇 ^目 third tower 146 pressure can be From 0. to 510 kPa, such as from ikpg 475 kPa or from 1 kPa to 375 kPa. In some embodiments, the third column 146 can be operated at a vacuum below 7, such as below 5 kPa or below 2 kPa. Reducing the operating dust force substantially reduces the column diameter and the reboiler negative cut of the third column 146. 1 The example components of the ethanol mixture stream and the residue components of the third column 146 are found in Table 32 below 201247300 7. It should be understood The distillate and residue also contained other components not listed in Table 7. Table 7: Concentration (wt.%) Light Hydrocarbon Tower (146 Figure 6) Concentration (wt.%) Concentration (wt.%) Three distillate Ethanol 70 to 99 72 to 90 75 to 85 ethyl acetate 0.5 to 30 1 to 25 1 to 15 acetaldehyde < 15 0.001 to 10 0.1 to 5 water < 10 0.001 to 2 0.01 to 1 tough acid · < 2 0.001 To 1 0.01 to 0.5 third residue ethanol 80 to 99.5 85 to 97 90 to 95 water < 8 0.001 to 3 0.01 to 1 ethyl acetate < 1.5 0.0001 to 1 0.001 3. 0.5 acetic acid < 0.5 < 0.01 0.0001 To 0.01 In some embodiments, water may be present in the distillate 131, which may be carried to the ethanol product stream 148. In one embodiment, water can be removed prior to recovery of the ethanol product. In one embodiment, the overhead of the conduit 131 can include less than i5 wt°/. Water, such as less than 1% by weight of water or less than 8% by weight of water. The distillate in line 131 can be fed to a water separator, which can be an adsorption unit, membrane, molecular sieve, extraction steam column, or a combination thereof. In one embodiment, at least 5% of the second substrate of line 131 is condensed and can be fed directly into third column 146. Fig. 7 is a flow chart showing the combined use of the reactive distillation column 141 and the ethanol product column 146. In this flow chart, the second museum output 131 is fed to the ethanol product column 146 and the second residue 132 is fed to the reaction vapor column 141, respectively. As a result, purified ethanol was recovered as the first residue in the line Mg and ethyl acetate was recovered as the third distillate 147 and recycled to the first test 107. The second residue 132 is fed into the reactive distillation column 41 to react the acetic acid in the second residue with methanol to produce cerium acetate, which is recovered in the line (4). The aqueous stream is recovered as a fourth residue which may include some acetic acid and is returned to the first column 1 to be used as a solvent. 33 201247300 The person is: ==== acid B: ―, better is more favorable. From the dll 'return some of the first - return to the reactor ι〇3 may be fine = to m acid / / (10) can be further in the hydrogenation reaction (10) and the reactor can be fed into the reactor Or feed into the steam to recover extra ethanol. Line 117ΦΜ * "The water must be removed from line 117. The water may be removed, for example, by an adsorption unit, one or more membranes, from the rim 7; for example, an adsorption unit may be used ( Not shown) Refined light flow with =ΐΐ=r5wt% water. Can be removed to at most ".99%, and better remove water from the first - to简%. Refined (d) liquid flow or part thereof can be returned to the reaction fine. Further one of the first hall of the eight-line m or one part of the liquid flow or two liquid flow can be yan / junjun liquid and acetic acid containing acetic acid This allows a portion of the hydrazine-containing liquid stream to be recycled to the reactor (10) while removing other liquid streams. The aspirating liquid stream has a value as a source of acetic acid s and/or (10). The tower may include any which may be required = each tower preferably includes a plate tower having (1) the number of bays, such as the number of female contacts, from if3菽0 to 75. The plate may be a sieve plate, a fixed valve plate, Movable valve plate or any other suitable design known to it. For other specifics, a packed tower can be used. The number or filling of the machine 1 may be arranged in one continuous tower or it may be arranged in two or more towers, so that the first segment from the first segment can enter the third segment and the second segment from the second segment Etc. '', the condensers and liquid separation vessels that can be used with the steaming towers can be of any conventional design and simplified to the towel. The Shantike money pair follows the drum refilling Heat applied at the bottom of the soil. Other types of transfer can be used, such as internal reboiling. Provided to 34 201247300 The heat of the reboiler can be derived from any heat generated during the process of integration with the reboiler or from external sources such as other heat generation. Chemical process or heat of reboiler. Although a reactor and a flasher are shown in the drawings, additional reactors, flasher 'condensers, heating elements, and other components may be used in various embodiments of the invention. It is well understood by the art that various condensing nu-condensing machines, such as a nano-connector, a separation vessel, etc., which are generally used for chemical processes, can also be combined and used in the process of the present invention. The temperature and pressure used in the column can vary. In each district The temperature is generally in the range between the composition removed by the distillate and the boiling point of the composition removed as a residue. As is well known to those skilled in the art, the temperature of the steamed mosquito is in contact with the touch. The material composition and the pressure of the column are determined. Further, the feed rate may vary depending on the size of the manufacturing process and is generally referred to as the feed weight ratio if described. The distillates in lines 119, 128, and 131 include ethanol as described above. And further using a plurality of additional separation systems such as steaming strips (such as completion towers), pressure swing adsorption systems, membranes, molecular sieves, extraction fines, or combinations thereof to purify the anhydrous ethanol product stream, that is, "complete waterless Ethanol". Any compound that is contained in the crude anti-knocking material from the feedstock is usually retained in the ethanol feedstock in an amount less than 〇lwt% of the total weight of the ethanol pavilion composition, such as less than 0.05 sense or less fox 02 pain. In one embodiment, one or more side streams can remove impurities from any of the columns in system 100. Preferably, at least one side stream is used to remove impurities from the third column. The impurities can be removed and/or confined within system 100. Q ', the completed ethanol composition produced by the process of the present invention may be taken from the third residue in the pipeline (10) from the third residue of the pipeline 119, (3) or the second distillation distillate 'line 128. Things. The ethanol product can be industrial grade ethanol or fuel grade ethanol. The range of ethanol compositions is shown in Table 8 below. 35 201247300

Ethanol 85 to 99.9 water <12 acetic acid <i ethyl acetate <2 acetal 1 < 0.05 acetone <0_05 isopropyl alcohol < 表.5 Table 8 ·· Complete ethanol composition 9 90 to 99.5 0.1 to 9 concentration (wt.%) 92 to 99.5 < 0.1 < 0.5 < 0.01 < 0.01 < 0.1

0.5 to 8 < 0.01 < 0.05 < 0.005 < 0.005 < 0.05 < 0.05 t of the 70% ethanol composition preferably contains a very small amount, such as less than 0, other alcohols 2 sterols ▲ alcohol, different Alcohol, isoamyl alcohol and other C4_C full classes. In a specific example, the amount of isopropanol in the finished ethanol composition is from 8 (ml 000 vwm, such as from 95 to t〇〇〇W^m, from 100 to 70 〇 wppm, or from 150 to 500 wppm. In the completion, the ethanol composition is substantially free of ", as the case may be, less than 5wppm or less than iwppm. The finished H-forms obtained by the specific examples of the present invention can be used in various ways. , including: fuel, solvent, chemical raw materials, pharmaceutical products, detergents, granules, hydrogen storage or hydrogen consumption system. Wei materials, finished alcohol fields can be combined with steam for vehicles such as > Cars, boats and small piston engine aircraft. In non-fuel applications, this complete ethanol composition can be used as a solvent for sanitary and cosmetic preparations, detergents, disinfectants, coatings, inks and pharmaceuticals. The processing solvent can be used as a manufacturing process for pharmaceutical products, food preparations, dyes, photochemicals, and latex processing. The finished ethanol composition can also be used as a chemical raw material to manufacture other chemicals such as vinegar, ethyl acetonate, Ethyl acetate, B , glycol ether, ethylamine, categor, and higher alcohols, especially butanol. In the manufacture of ethyl acetate, the finished ethanol composition can be esterified with acetic acid. In other applications, the completed ethanol composition can be Dehydration to produce ethylene. While the invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. In addition, this disclosure and/or the accompanying claims 36 201247300

The knowledge of 1 ® Θ 斤 述 本 本 本 本 本 本 本 凫 凫 凫 凫 凫 凫 凫 凫 公 公 公 公 公 公 。 。 。 。 The invention is made. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be more fully understood by reference to the description of the accompanying drawings. Fig. 1 is a schematic view showing an ethanol production system having a distillation column for recovering a dilute acid stream as an extractant from acetic acid according to the present invention. Fig. 2 is a schematic view showing an ethanol production system having a distillation column for recovering a dilute acid stream as an extractant from ethanol according to an embodiment of the present invention. Fig. 3 is a schematic view showing an ethanol production system having a distillation column for recovering a dilute acid stream suitable as an extractant according to an embodiment of the present invention. Figure 4 is a schematic view of an ethanol production system having a steam column for recovering an extractant according to an embodiment of the present invention, using one or more water separation devices to separate acetic acid to be returned to the reactor and to be used as The water returned by the extractant. Fig. 5 is a schematic view showing an ethanol production system having a steaming tower for recovering an extractant and an esterified soap element according to an embodiment of the present invention. Fig. 6 is a schematic view showing an ethanol production system having a distillation column for recovering a dilute acid stream and other columns for separating ethyl acetate and ethanol according to an embodiment of the present invention. Fig. 7 is a schematic view similar to the ethanol production system of Fig. 6 according to an embodiment of the present invention, which has an esterification unit in a reactive distillation column. [Main component symbol description] Code description 100 System 37 201247300 Code description 101 Reaction zone 102 Separation zone 103 Reactor 104 Hydrogen feed line / line 105 Acetic acid feed line / line 106 Separator 107 First column / Extraction column / tower 108 Second column/acid column/diluted acid recovery column 109 Third column/tower 110 Vaporizer/exhaust line 111 Line 112 Line 113 Liquid stream 114 Steam stream 115 Extractant 116 Line/first residue 117 Line 118 Line 119 Line 120 Line 121 line 122 second column 123 line 124 line 38 201247300 code description 125 fresh extractant 126 line / third column 127 line 128 third distillate 129 second column 131 second distillate 132 dilute acid stream 133 134 Second Tower 135 Line 136 Line 138 Water Separator 139 Line 140 Line / Acetic Acid Stream 141 Third Column / Light Hydrocarbon Tower / Reactive Distillation Column / Esterification Unit 142 Line / Methanol Feed Stream 143 Line / Third Distillate Discharge 144 Third Residue Stream 146 Third Column / Ethanol Product Column 147 Ethyl Acetate Recycle Stream 148 Line 39

Claims (1)

201247300 VII. Patent Application Range: 1. A process for producing ethanol, comprising: hydrogenating acetic acid from an acetic acid feed stream to form a crude ethanol product in a reactor +; at least a portion of the crude ethanol product in a = column Separating into a first-distillate comprising ethylene and acetoxime acetate and a first product comprising ethanol, acetic acid, water and acetic acid; f is the same as the crude ethanol product feeding point Leading to the first column; and recovering ethanol from the first residue. ^中π专利|_Process of the first item 'where the dilute acid stream comprises less than 3Q% by weight of acetic acid 0 3. 4. 5.6. 7. 8. 9. Patent scope of the process, wherein the dilute acid stream Includes water. The process of any of the items, wherein the first residue is separated into a process of the patent scope, wherein the dilute acid stream is continuously fed into the process of the first column - wherein the dilute acid flow system In the process of the enclosure, wherein the dilute acid stream comprises a concentration of water at least about equal to the concentration of water in the product of the precursor. In the process of applying for the patent __ item, wherein the process of converting acetic acid in the reactor is large, the recovery includes: Near the first 10. The tooth is out of the package: water = 2 = residual = raw includes ethanol and Acetic acid - the second === one of the first tower: and the application for the nine items of the special profit, the towel is derived from the second, as in the application of the patent (4) 9 and 1G residual items The process, further comprising separating the second residue of at least 11.2〇12473〇〇 to form a water stream and an acetic acid stream. 12. The process of any of clauses 9 and 5, further comprising returning at least a portion of the acetic acid stream to the reactor or returning to the first column as an extractant. 3. The process of any one of claims 9, 10, 11 and 12, wherein the water separator used for separating the first residue is selected from the group consisting of an adsorption unit and a membrane. H. The process of any one of clauses 9, 1 , n, and 3, wherein the method further comprises: causing at least acetic acid from the second residue to be selected from the group consisting of methanol and ethanol An alcohol is reacted in the esterification unit to produce at least one ester and water; separating the at least one ester from water to produce an ester product stream comprising at least one ester and a bottoms stream comprising water; and at least a portion of the The bottoms stream is returned to the first column as an extractant. 15. The process of any one of clauses 9, 10, 11, 1, 2, 13 and 14, further comprising separating at least a portion of the second take-up, resulting in a third comprising acetic acid Distillate and a third residue comprising ethanol.