TW201247301A - Extractive distillation of crude alcohol product - Google Patents

Abstract

Recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid using an extractive distillation column. The column yields a first residue that comprises ethanol, ethyl acetate, acetic acid, and water. The first residue is separated in a second column to yield a second distillate comprising ethanol and ethyl acetate. The second distillate is then separated in a third column to yield a third distillate comprising ethyl acetate and a third residue comprising ethanol.

Description

201247301 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; U.S. Patent Application Serial No. 13/094,641, filed on Apr. 26, 2011, and No. 13/162, No. 34, 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 a process for recovering ethanol from extractive distillation. [Prior Art] The traditional production method of ethanol used in industry is from petrochemical raw materials, such as petroleum, natural gas, charcoal, or from injection problems, such as reduction or reduction, or (four) materials or fiber materials, such as corn or Lai. It has traditionally come from petrochemical feedstocks and fiber raw materials to produce B-methods - hybrid hydration, methanol colloidal reactions, direct alcohol synthesis and, Fischer_Tr〇psch synthesis. Instability ^ The price of the shoulder material will cause the cost fluctuation of the traditional way of producing ethanol. #The raw material price on Pan = will make it possible to substitute the source to produce B. The demand is more riding, the powder raw material and the cellulose raw material can be fermented into ethanol. However, the fermentation method Usually used in consumer ethanol production, ϊΐίϋΐϊί can be used for fuel or human consumption. In addition, the fermentation of the powder or fiber 2 will compete with the food source, thus limiting the amount of ethanol that can be used in industrial production. The reduction of saccharides and/or their domain-based compounds for the production of ethanol has been extensively studied, 201247301, and various catalysts have been mentioned in the literature. The combination and operating conditions of the support. When alkanoic acid (e.g., acetic acid) is reduced, other compounds are formed with or formed by a side reaction which limits the production and recovery of ethanol from such a reaction mixture. In the hydrogenation process, esters, ethanol and/or water are produced together to form an azeotrope, which is difficult to separate. In addition, when the conversion is incomplete, 'unreacted acetic acid still remains in the reactor product. And it must be removed to recover ethanol. European Patent EP02060553 describes a process for the conversion of hydrocarbons to ethanol, which involves converting hydrocarbons to acetic acid and then hydrogenating the acetic acid to obtain ethanol. Separating the stream from the hydrogenation reactor, In order to obtain a stream of ethanol and a stream of acetic acid and ethyl acetate, the stream is recycled to the hydrogenation reactor. U.S. Patent No. 7,842,844 describes the conversion of hydrocarbons to ethanol in the presence of a particulate catalyst and optionally converted to In the reaction of acetic acid, it can improve the selectivity, the activity of the catalyst and the service life of the catalyst. (4) Steps. Others have proposed various extractants for separating ethanol, acetic acid, and water. U.S. Patent No. 4,654,1Z3 describes a process for separating ethanol from water by using an extractant. U.S. Patent Nos. 4,379,028 and 4,569,726 describe the use of extracts to recover ethyl acetate from a mixture of ethyl acetate/ethanol/water. U.S. Patent No. 6,375,8,7 is described by A method for separating ethanol and ethyl acetate by an extracting agent, and there is still a need to improve a process for recovering ethanol from a crude product obtained by, for example, a reduction of the silk compound, and/or a silk compound thereof. - In the embodiment, the present invention is directed to the production process of Lin, which comprises from the reaction of the chemical processing, and the production of the coarse flow technique 2 or the extraction, the separation of at least part (10) Crude product: the first residue of the acetaminophen acetate series, and the first residue containing various extractants of ethanol and vinegar, and the extractant is selected from water, dimethyl 2 4 201247301 (dimethylsulfoxide) ),glycerin, Glycol,! _ phenol, hydroquinone, hydrazine, Ν '_: mercaptocarbamide, 1,4-butanediol, glycol 丨, 5-pentanediol, propylene glycol _ tetraethylene glycol _ polyethylene glycol , glycerol-propylene glycol-tetraethylene glycol _1,4-butanediol, diethyl ether, formic acid, brewing, cyclohexyl, N,N, dimethyl-propylamine, N,N'-dimethylethylene A group consisting of amine amines, diethylenetriamine, hexamethylenediamine, oxadiamine pentane, alkylthiophene, dodecane, tridecane, tetradecane, gasified paraffin, and mixtures thereof. In one embodiment, the first residue may comprise less than 5% by weight ethyl acetate. The process further includes separating at least a portion of the first residue in the second distillation column to produce a second distillate comprising ethanol and ethyl acetate, and a second residue comprising one or more extractants. The first pavilion of the mouth P knife produces a third take-up containing ethyl acetate and a third residue containing ethanol. At least part of the second residue of the embodiment cap is returned, the first steaming, as one or more extractants, and the second residue may comprise less than 3% by weight acetic acid. In the implementation of the towel, the steaming age can be operated at a pressure below the level, for example below 50 kPa, or below 2 kPa. In a second embodiment, the present invention is directed to a process for producing ethanol comprising the steps of: providing a crude ethanol product comprising ethanol, acetic acid, ethyl acetate, and ethyl acetate; In the first-seam column, the crude product of at least part of the ethanol is present in the presence or absence of extraction, and comprises (4) and ethyl acetate, and comprises ethanol, ethyl acetate, and one or more extractants. a first residue; separating the first residue in a steaming tower to produce a second precipitate comprising ethanol and ethyl acetate; a second residue comprising: one or more extractants' and separating at least - Part of the first product, resulting in a third drug comprising ethyl acetate, and a third residue comprising ethanol. In the present invention, the present invention is directed to a process for producing ethanol, which comprises the following steps: hydrogenation of acetic acid in a acetic acid feed stream in a reactor to form a crude ethanol product - distillation in the presence of water extraction At least - part of the private product ^ = and: the first, the output of the acid vinegar 'and contains ethanol, water: 3 in the second steaming scale to separate the first residue, resulting in a second containing ethanol residue = human water and acetic acid Residues, and recovering from the second museum's and '201220121. In the embodiment, the process may include separating at least a portion of the second residue to form an aqueous material k and an acetic acid I acetic acid stream. The stream is returned to the first steaming tower 7 as an extractant. The adsorption device, the separation enthalpy, the digestion, and combinations thereof may be used to separate the water and the acetic acid. In another embodiment, the process further comprises at least the alcohol of the = and the second residue in the acetating unit (preferably The reaction is methanol) to produce at least one vinegar and water, and at least one vinegar is removed from the water to produce a vinegar product stream comprising at least one vinegar, and an aqueous stream comprising water. The aqueous stream is returned to the first distillation column as an extractant. In a fourth 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 a first steaming tower Working under the water extracting subdomain and at a grinding force below 7G kPa, for example below 5 〇 kPa ' or below 20 kPa, separating at least a portion of the crude ethanol product to form a chain comprising ethyl acetate and ethyl acetate _The first library, and the first residue containing ethanol, water and acetic acid; the first residue is separated at the second steaming age to produce a second museum containing ethanol, and a second containing water and acetic acid The residue is recovered from the second distillate. In particular, the present invention relates to a process for recovering ethanol obtained by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction produces a crude ethanol product comprising ethanol, water, acetic acid, acetic acid, and other impurities. Since ethyl acetate was similar to ethanol, the ethyl acetate was separated from the mixture of ethyl acetate and ethanol by distillation. The presence of other components in the crude ethanol product, such as the presence of ethyl acetate, acetic acid and acetaldehyde, further complicates the separation of ethanol and ethyl acetate depending on the concentration. In order to improve the efficiency of recovering ethanol from the crude ethanol product, the process of the present invention involves recovering ethanol from the crude ethanol product by one or more extractants in an initial (first) separation distillation column. Ethanol, water and acetic acid were pipetted as a residue. Ethyl acetate and other light organics were pipetted as a distillate. The presence of the extractant allows the ethanol product to be more efficiently separated from the ethyl acetate by-product. Most of the ethyl acetate can be recovered from the crude ethanol product using an extractant in accordance with an embodiment of the present invention. Preferably, at least 9% by weight of the crude ethanol product, for example at least %% or to 6 201247301 /, 98/6 of ethyl acetate is used to recover most of the acetic acid via the first -|g product Ethyl vinegar can make the ethyl acetate in the residue from the initial steaming tower low concentration, for example, less than i% by weight, less than 0.3 wei or lower than the weight. The ethanol product having a reduced content of acetic acid can be recovered by the production or the extraction. Preferably, at least 5% by weight of ethanol is present in the crude ethanol product, and particularly preferably at least 90% of the ethanol is recovered in the first residue stream. Advantageously, this separation process using an extractant results in reduced energy requirements in the operation of recovering ethanol from the crude ethanol product. The extractant used in the present invention may vary. Preferably, the extractant has a higher boiling point than the main component of the distillate. In the preferred embodiment 10, the extractant used has a boiling point above 80 ° C, such as above 85 ° C, or above 1 Torr. Hey. An extractant having a boiling point higher than 2 〇〇〇c can also be considered. A preferred extractant includes water. Water can be produced in the hydrogenation reactor and recovered as an extractant. Preferably, at least one of the extractants is a by-product of the process for producing ethanol from hydrogenated acetic acid. By using by-products as an extractant, the cost of addition and recovery of the extractant can be reduced. In one embodiment, the by-product is water&apos; and the water is purified by removing ethanol and/or acetic acid. The purified water can reduce the recovery of other components in the distillation column which will cause side reactions, such as a water separation device, such as an adsorption device or a separation membrane, or an esterification unit that reacts acetic acid can be used to purify water. Purification of the water also allows the recovery of acetic acid, which can be returned to the reactor. In another embodiment, the by-product water can be part of a dilute acid stream without the need for enhanced purification. Although not limited to dilute acid streams, when hydrogenation achieves a high conversion of acetic acid, above 80% 'more than 90% or above 95%, a dilute acid stream is preferred. Therefore, the dilute acid stream can reduce the overall energy demand while maintaining efficient separation in the initial distillation column. The dilute acid stream may comprise at least 40% by weight of water 'e.g., at least 60% by weight of water, or at least 8% by weight of water. The dilute acid stream can comprise acetic acid. For example, the extractant may comprise less than 30% by weight, such as less than 20% by weight 'less than 1% by weight or less than 5% by weight of acetic acid. Without being bound by theory, the acetic acid in the dilute acid stream is not necessarily an extractant, and the extractant can reduce the amount of ethanol, water, and/or acetic acid carried into the distillate of the initial distillation column. Other suitable extractants may also be used, including, for example, dimercaptopurine, glycerin, digan 201247301 alcohol _ 1 naphthol, hydroquinone, N, N, _: methyl ketoamine, i, 4 _ Glycol, glycol-indole, 5-pentanol-propanol-tetraethylene glycol_polyethylene glycol, glycerol-propylene glycol tetraethylene glycol-1,4-butanediol, diethyl ether, acid methyl hydrazine, ring Burning, N,N,-dimethyl-1,3-propanediamine, N,N'-dimethylethylenediamine, diethylamine-amine, hydrazine, 3-diamine pentane, alkylation Porphin, dodecan, tridecane, tetradecane, gasified paraffin, and mixtures thereof. These other extractants can be formulated with water. Some suitable extractants include those described in U.S. Patent Nos. 4,379, 〇28, 4, 569, 726, 5, 993, 610, and 6, 375, 807, the entire disclosures of which are incorporated herein by reference. In an embodiment, the extractant can be fed to an initial distillation column to treat the crude ethanol product. In the embodiment, the extractant is fed first and combined with the crude ethanol product, and the initial steaming is introduced. Preferably, most of the ethanol, water and acetic acid are removed from the crude ethanol product as residues from the initial steaming tower. Things. The residual stream, for example, may comprise from 30% to 99.5 per cent of water in the crude ethanol product, and unpredictable (8) fine impurities. The residue may comprise extract and water, and f may have a higher concentration of water in the residue than in the crude ethanol towel. For example, with the separation tower outside the multi-steel, the paste can be shouted from the touch of wealth, and sent back to the original. Generally speaking, the output from the original steaming tower can contain all or part of the acetic acid. . In the 4th embodiment towel, the gallery output of :::: may further comprise ethanol and preferably less than 15% by weight of water, less than Μ 0, 7, less than 4% by weight of water or less than 2 The % by weight of the extractive column is taken from the distillate to Wat &amp; another stroke of the steaming step to the output of acetic acid, and the lightly proud steaming tower can be used for the inlet and outlet. w ah s s day flow and ethanol flow 'and the acetic acid B S stream to the hydrogenation counter-step 3 = t application method can generally reduce the amount of ethyl acetate in the residue, but because of the second production: Two substances: any ethyl acetate is preferred as ethyl acetate

For 50 weights of alcohol, it is possible to separate the acetic acid lion from the E-residue 8 201247301 = the separation of the substance can be sent _ initial _ tower, and removed as the first museum species return _ acid B The stream can be sent to the initial steaming tower below the extractant feed location. The material rmr is used in any hydrogenation process to produce ethanol. The materials, the lining, the reaction conditions and the separation process which can be used for the hydrogenation of acetic acid are described below. This is used in the present invention for the remainder of the material, minerals and silk, which can be produced from any suitable source, = gas, petroleum, coal, biomass, and the like. For example, acetic acid can be produced by methylation, acetic acid oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. A ruthenium-based process suitable for the production of acetic acid is described in U.S. Patent Nos. 7,208,624, 7,115,772, 7,005,541 ^ 6,657,078 &gt; 6,627,770 &gt; 6,143,930 ^ 5,599,976 ^ 5,144,068 ' 5,026,9G8, 5 Hui, 259 and 4,994,6G8, all It is revealed that the ethanol production can be integrated with these methanolization processes. Optionally, ethanol production can be integrated with this methanol filamentization process. As oil and natural gas prices fluctuate, the use of alternative carbon sources to produce acetic acid and methods such as methanol and carbon monoxide has attracted increasing interest. In particular, it can be advantageous to produce acetic acid when the stone / 'synthesis gas from the price of natural gas is more south than by any suitable carbon source." For example, a method of modifying a methanol plant to produce acetic acid is disclosed in U.S. Patent No. 6,232,352, the disclosure of which is incorporated herein by reference. By modifying the methanol plant, it is possible to significantly reduce the capital cost of the new vinegar and the carbon dioxide associated with it. Derived from a methanol synthesis loop produces all or a portion of the syngas, which is supplied to a separator for carbon monoxide, which is then used to produce acetic acid. In a similar manner, the hydrogen in the hydrogenation step can be provided by a combination. In some embodiments, some or all of the feedstock in the above-described acetic acid hydrogenation process may be derived from syngas. For example, acetic acid can be formed from methanol and carbon monoxide, both of which can be derived from syngas by partial oxidation reforming or thief reforming to form syngas, and - carbon monoxide can be separated from the syngas. Similarly, the hydrogen which forms the crude ethanol product from the hydrogenated acetic acid can be separated from the synthesis gas. Accordingly, the syngas can be from a different carbon source. The carbon source, for example, may be selected from the group consisting of city gas, crude oil, petroleum, coal, biomass, and combinations thereof 201247301. Syngas or hydrogen can also be obtained from biologically derived reduced bodies, such as biologically derived methane gas produced by landfills or agricultural waste organisms. Compared to; ε-fuels such as coal or natural gas, the bio-derived syngas contains a detectable 14c isotope. There is a balance between the new formation of the Earth's atmosphere and the constant decay of the Wei, and therefore the proportion of the mc core in the carbon nuclei in the atmosphere on Earth is long-term constant. Since the living organic system exists in the air, the same score WM_14C:12C&amp; will be established in the living organism' and this distribution will stop changing when the living organism dies, but the MC will decompose with a decay of about 6,000 years. (iv) Acetic acid and/or sulphur is formed from syngas derived from biological materials and is expected to have a substantially similar HC content to living organisms. For example, the 14c:12c ratio of sterol, acetic acid, and/or ethanol can be 14C: of the living organism, in the range of 〇5 to about i. In other embodiments, the syngas, methanol, acetic acid, and/or ethanol are all derived from a fossil fuel 'also' from the carbon source produced by 6G'GGG years ago, and there is no glycerable 14c. Content In another embodiment, the acetic acid used in the hydrogenation step can be formed from the fermentation of the biomass. Preferably, in the fermentation process, acetic acid is produced by fermentation using an acetogen Jc process or by homoacetogenic microorganisms, and if present, there are few as by-products. carbon dioxide. The carbon efficiency of the fermentation process is preferably higher than 7〇%, and higher than 8〇 is higher than 9〇%. The yeast process generally has a carbon efficiency of about 67%. Optionally, the microorganisms of the lining fermentation process are __Jian (Qingru) selected from the group consisting of fusiform buds, stalks g, Morerads, stalks, larvae, propionic acid, propionate a group consisting of Clostridium clostridium, Gram-negative anaerobic bacteria, and Mycelia, and especially species selected from Clostridium malic acid, Clostridium butyricum, and Clostridium thermophilus 1 Chivi's thermophilic anaerobic _, Debruchi lactic acid bacteria, propionate fine sputum, propionic acid serotonin, Susinick anaerobic bacteria, lactic acid bacteria and endoglucanase groups. Optionally, in this process, all or part of the unfermented residue from the main material, such as lignans, can be gasified to form hydrogen, which can be used in the steps of the present invention. A typical fermentation process for the formation of acetic acid is disclosed in U.S. Patent No. 6,5,9,18, the entire disclosure of which is incorporated herein by reference. See also U.S. Patent Application Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are incorporated herein by reference. For example, biological materials may include, but are not limited to, agricultural waste, forest products, grass and other cellulosic materials, wood harvest residues, softwood chips, hardwood chips, branches, stumps, leaves, bark, ore chips, substandard pulp, corn. , corn stalks, wheat knots, straw, stalks, stalks, grass, animal waste, municipal waste, urban domestic sewage, commercial waste, grape residue, shell, walnut shell, coconut shell, coffee residue , grass particles, grass balls, wood balls, cardboard, enamel, return and cloth. In addition, the bio ride is an aqueous solution of wood residues, hemicellulose and inorganic chemicals. U.S. Reissue Patent No. RE35,377, which is incorporated herein by reference, which is incorporated herein by reference in its entirety in its entirety in the the the the the the the the This process 匕3 is a moxibustion of a solid and/or liquid carbon material to obtain a process gas, which is formed by additional weaving to form a syngas. The synthesis gas is converted to methanol. The sterol is then obtained by brittle. The method can also generate nitrogen gas with the lion, and f can be used in the invention of the four patents of the present invention as described above, which discloses a process for converting waste biomass into gasification by gasification, and discloses a nitrogen-containing body composition in the United States (4) (10) 5,754. The preparation of a product such as a synthesis gas comprising hydrogen and carbon monoxide is incorporated herein by reference. - The acetic acid fed to the hydrogenation reaction may also contain other carboxylic acids and their anhydrides, as well as acetaldehyde and = hydrazine. Preferably, a suitable acetic acid feed stream comprising one or more compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These other compounds can also be hydrogenated in the process of the present invention. In some embodiments, the presence of a carboxylic acid, such as propionic acid or an aldehyde thereof, can be beneficial for the production of propanol. Water can also be present in the acetic acid feed. Further, acetic acid in the form of a vapor from a flash tank of a methanol carbonylation unit as described in U.S. Patent No. 6,657,078, which is incorporated herein by reference in its entirety, 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 acetic acid and light ends' or remove water, thereby saving overall processing costs. 201247301 Acetic acid can be evaporated at the reaction temperature. Subsequent evaporation of acetic acid can be fed to the reactor along with undiluted nitrogen or hydrogen diluted with a relatively inert carrier gas such as nitrogen, argon, helium or carbon dioxide. In order for the reaction to operate in the gas phase, the temperature in the system should be controlled so that the temperature is not below the dew point of acetic acid. In one embodiment, acetic acid can be vaporized at the boiling point of acetic acid at a particular pressure. The then evaporated acetic acid can be further heated to the reactor inlet temperature. In another embodiment, the acetic acid is mixed with other gases prior to evaporation and the combined vapor is then heated to the reactor inlet temperature. Preferably, the hydrogen and/or recovery gas is passed through the acetic acid at a temperature equal to or lower than 125 ° C to transfer the acetic acid to a vapor state, and then the combined gas stream is heated to the reactor inlet temperature. A number of configurations can be used in some embodiments of the hydrogenation of acetic acid to form an ethanol process, including fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, an adiabatic "reactor" can be used; that is, in such embodiments, there is little or no need to pass an internal conduit into the reaction zone for heat addition or removal. In embodiments, a radial flow reactor or a reactor set may be used, or a series of reactors may be used, with or without heat exchange, quenching or introducing more feed. A shell and tube reactor having a heat transfer medium is used. In many cases, the reaction zone can be disposed within a vessel or a series of vessels (sets) in which the heat exchanger is interposed. In a preferred embodiment, the catalyst For use in a fixed bed reactor, the reactor, for example in the form of a pipe or tube, wherein the reactants are typically passed in the form of steam or passed through a catalyst. Other reactors may be employed, such as fluidized or bunk bed reactors. 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 reactants with the catalyst particles. The argonization reaction can be carried out in the liquid phase or in the gas phase. Preferably, the reaction is carried out in the gas phase under the following conditions: The reaction temperature can be between 125 ° C and 350 ° C, for example: from 2 〇〇. To 325. (:, from 225C to 300C ' or from 250 ° C to 300 ° C. Pressures range from 1 〇 kPa (kpa) to 3, 〇〇〇 kPa, for example. From 50 kPa to 2,300 kPa , or from 1 kPa to ^500 kPa. The "vapor hourly space velocity" of the reactants fed into the reactor, (GHSV) can be higher than at least 5 〇〇 / hr, Example 12 201247301 eg higher than At least feet/hour, above at least I·hour, even above the range, GHSV can be from material time to 5_hour, for example: (four) / ^ to 3::, hour, hour to 10._ / hour , or 丨, _, although the reaction will consume two moles of hydrogen per mole of acetic acid, and the actual molar ratio of hydrogen to acetic acid in the feed stream may be different from the ethanol produced in the feed stream, from ι〇 〇·(4). 100, for example, from 50: mountain··5〇, from 20:...:2, or from 18:(f): work. The difference between contact or stagnation depends on acetic acid f, catalyst, reactor The temperature and the amount of pressure. The number of the contact _____ is small. On the catalyst system other than the fixed bed, the contact time of the phase reaction is preferably from αιsec to ι〇〇sec. It is carried out in the presence of a hydrogenation catalyst. Typical catalysts are described in U.S. Patent Nos. 7,6,8,744 and 7,863, and U.S. Patent Application Serial No. Wio/omm and 2〇10/ 0197985, the entire contents of which are hereby referred to. In the other embodiment, the 'catalyst system US special shot, please disclose the start/face/sulfur type catalyst described in Wei 2_/_6()9, the entire contents of which are here. In some embodiments, 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, and nickel. Groups of 钌, 钌, money, exempt, iron, record, New Zealand, titanium, zinc, road, scorpion, turn and crane. Preferably, the first metal is selected from the group consisting of flipping, turning, inscription, recording, and sputum. As noted above, in some embodiments, the catalyst further comprises a second metal that will generally act as a promoter. If present, the second metal is preferably selected from the group consisting of copper, molybdenum, tin, iron, knot, slave 'tungsten, put, start, net 'decoration, fierce, 钌, 铢' gold and recorded, and . More preferably, the second metal is selected from the group consisting of copper, tin, cobalt, rhodium, and nickel. If the catalyst comprises two or more metals, such as a first metal and a second metal, the f-metal can be used in an amount from 0.1 to 5% by weight, for example from 0.1 to 5% by weight, or from 0.1 to 3 by weight. ^. The second metal is preferably used in an amount of from 0.1 to 20% by weight, for example from 0.1 to 10% by weight, or from 〇·1 to 7.5% by weight. 〆13 201247301 The best metal combinations in the peak and middle include the touches of '钌, 铢, 、, 纪金 简, green, her, copper (four) third metal, the third metal can be selected from any of the above-mentioned gold-like I,ini 'To be the third gold shot is the same as the first metal and the second metal. In a group such as 2fr..., 钌, copper, rhetoric, tin, and chain, except for ί ^. In one embodiment, the catalyst may be white, tin, and australis. In addition to the metal, in the present invention - in some embodiments the catalyst is further ===. Difiedsupp呤 is used in this article. Ί系 k 3 Continued miscellaneous materials and 敎 敎 继 继 继 继 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ To, or the weight of the lion is 97.5 weight. ΪΪ _ body, such as dioxotomy, oxidized Wei Huaming, Dai Shishi:: branch =, pyrolysis dioxide dream, high purity dioxide Wei mixture. The dragons include, but are not limited to, iron oxide, oxidized |g, dioxane, oxidized, magnesium oxide, graphite, cerium surface area graphitized carbon, activated carbon, and mixtures thereof. The selected body can be a very plastid, and its technical formula has a quantitative effect (4) heavy Wei, =^=%, from 1 to 2 〇 heavy Wei, or 3 to 15 wei, the percentage is in some embodiments 'Support modifier can be an acidic modifier, which can increase the acidity of the catalyst. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Group metal oxides, ... metal oxides of the family: the group of the domain of the mixture of the oxidizer. Acidic modifiers include those selected from the group consisting of 2), oxygen (Zf〇2), Mithril (10), 卩 her (Ta you, alumina (ai2o3), oxidation shed (B2〇3), Bismuth pentoxide (p2〇5), bismuth oxide (four), oxidation 201247301 tungsten (W03), molybdenum oxide (Mo〇3), ferric oxide (Fe2〇3), chromium oxide (Cr2〇3) ), a group consisting of vanadium oxide (V2〇5), manganese dioxide (Mn〇2), copper oxide (Cu〇), cobalt oxide (c〇2〇3) or bismuth oxide (Bi2〇3). Preferred support modifiers include oxides of tungsten, molybdenum, and vanadium. In other embodiments, the support modifier can be an alkaline modifier having low or no volatility. An exemplary modifier, for example, may be selected from the group consisting of (丨) soil-measured metal oxides (11) metal oxides, (iii) alkaline earth metal bismuth salts, (5) alkali metal bismuth phthalates (v ) periodic table of lanthanide metal oxides, (vi) periodic table lanthanide metal bismuth citrate, (vii) periodic table lanthanide metal oxide '(νϋί) periodic table 1113 metal bismuth citrate, and its mixture Group of objects In addition to metabolites and other salts, other types of modifiers may also be used, including sulphate, nitrite, acetate and Wei salt. The hybrid support modifier is selected from the oxidation of Na's unloading, m- and zinc. And partial salt, as well as any of the above-mentioned mixtures, a preferred group of modified _ cut_, especially preferred is calcium metasilicate (CaSi03). Calcium metasilicate can be crystalline or amorphous (am The form of 〇rph〇us). The catalyst composition suitable for use in the present invention is preferably a metal i-egnatkm modified by a building body, but other processes such as chemical vapor deposition (ehemieal) This is also known in U.S. Patent Nos. 7,6,8,744 and 7,863,489, and to the United States, the disclosure of which is incorporated herein by reference. After drying and simmering, the catalyst can be activated. The reduction is carried out in the presence of a reducing gas, and the contact is carried out in the presence of the system. The initial ambient temperature rises to 400. (: The reducing gas is continuously passed through the catalyst. The hydrogenation reaction is carried out to carry out the reduction reaction. In particular, the acetic acid hydrogenation can achieve good acetic acid conversion rate and good selectivity to ethanol and yield. For the purpose of the present invention, "conversion rate", _ word means The acetic acid of the scale towel is converted into the amount of compound other than acetic acid. The conversion rate is expressed as the percentage of acetic acid in the feed. The conversion rate can be at least 4% or more 'for example, to at least 'fine%', to 対娜 or to 15 201247301 (4) The percentage of the mole of acetic acid in the gambling of the two sheets should depend on each type of 曰, transformation. The object has an independent selection rate, and the selection rate is also independent of the conversion rate. Example 2: After converting 6G mol% of acetic acid to ethanol, we mean that the selectivity of ethanol is 6〇%. The better is that the catalyst has a selectivity to ethanol of at least 6%, for example, at least listening, or up to 80%. Also preferred in the embodiments of the present invention is the selection of products that are not expected, such as the choice of a hospital, an ethylene bromide, and a carbon monoxide. The selectivity to these non-lin products is preferably low. At 4%, for example, less than 2% or less than 丨%. The "yield" is the number of grams of the reduced amount of towels per gram of the county, such as ethanol. The yield can be from 1 to 3 per gram of catalyst per kilogram of ethanol. In various embodiments of the invention 'Before any subsequent treatment, such as purification and separation, the crude ethanol product produced by the hydrogenation process typically comprises unreacted acetic acid, ethanol and water. The term "alcoholic acid" is used herein. "Product" means any composition comprising from 5 to 7 wt% ethanol and from 5 to 40 wt%. A typical composition range of the crude ethanol product is provided in Table 1. "Others, as defined in Table 1, may contain, For example, g is a class, a shout, a class, a class of ten hydrocarbons, and carbon dioxide. Table 1: Composition of crude ethanol product ! Degree (% by weight). Concentration (% by weight) Road... tongue order "Cleavage 70 z; , Production One" &quot;&quot;~ ------

201247301 In the embodiment, the crude ethanol product of Table 1 can have a higher conversion rate to form a low concentration of citric acid, and the concentration of the acetic acid can range from _% by weight to 2 (), for example, vinegar to 1 〇 wei , side to 5 interesting. In the lower style, it is preferred to reduce the brain __ scale by more than 75%, for example, above 9〇%. In addition, it is preferred that the selectivity to ethanol can also be higher, especially higher than 75%, for example, higher than 8 or higher than 9〇% η $ small in the *7 embodiment, 'ethanol to water The weight ratio may be at least 1818:1 or higher, for example, 〇 〇 .5 · 1 or at least 1 small, the weight ratio of ethanol to water may be from 〇.m to .1, for example, from 0.5. : 1 to 3 : 丨, or from 丨:i to 2 :. The crude soil alcohol product is superior to the traditional ethanol fermentation process. Because the ethanol content is higher than that in the embodiment, the lower water content requires less energy to separate the ethanol, and the overall efficiency is improved. Accordingly, in a preferred embodiment, the ethanol is from 1 to 5 wt% in the crude ethanol product, e.g., from 7 g wt% or from 25 wt% to 70 wt%. Particularly preferred is a higher weight percentage of ethanol. A typical ethanol scum according to an embodiment of the present invention is shown as the first ride. Each of the nitriding systems includes a suitable hydrogenation reactor and a process for separating ethanol from the crude mixture of ethanol obtained. System 100 includes a reaction zone 1〇1 and a separation zone 1〇2. Figures 2, 4, 5 and 7 illustrate the sinister purified water, which is a by-product of the extractant. Figures 3 and 6 illustrate a typical system for recovering a dilute acid stream as an extractant. As shown in Figures 1-7, the reaction zone 1〇1 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 evaporator 110 via lines 1〇4 and 1〇5, respectively, and a vapor feed stream is established at the official line 111 and directed to the reactor 103. The feed to reactor 103 contains fresh acetic acid. In one embodiment, lines 104 and 1 5 can be combined and fed together to evaporator γ, for example, containing hydrogen and acetic acid in a single stream. Preferably, the steaming/flying feed stream temperature in line 1U is from 100. c to 350. 0, for example, from 120. C to 310. C, or from 150. c to 300. (: Any unvaporized feed is removed from the evaporator 11 via a blowdown stream. Further, although the line 111 is shown as directed to the top of the reactor 1〇3 as shown, it can also be directed to the reactor 1〇3 Side 17 201247301 Side, upper or bottom. Has been used to hydrogenate carboxylic acid, preferably hydrogenated acetic acid, to form ethanol. In the embodiment, it can be used upstream of the reactor or any evaporator 11〇 One or more guard beds (not shown) are used upstream to prevent the catalyst from becoming fine to poisons or undesirable impurities contained in the feed or return/circulation streams. 4 guard beds can be used for unification 4 or liquid flow (1) Suitable protective bed materials may include, for example, carbon, dioxide, oxygen, or ceramics. In one aspect, the guard bed media is functionalized (WiGnalized), for example, silver functionalized to capture specific The species 'such as sulfur or self-supply. In the hydrogen donation, it is preferred to continuously withdraw the crude ethanol product from the reactor 103 through the line 112. 'The acetonitrile product in the line 112 can be condensed and transferred to the record (4) 6 In contrast, the vapor stream 114 and the liquid stream are provided by the separator. Separator 1〇6, for example, may include one or more flash towers or knoekout pots. The separation Hi-synthesis temperature can be from 2〇.〇 to %(rc 'eg 'from 3(rc to 32) Generation or from the 乂 to the 乂. The separator 1 〇 6_ force can be from 1 〇〇 kPa to 3, 〇〇〇 kPa, for example, from 125 kPa to 2,5 kPa or from (9) kPa Up to 2, 2 〇〇: Pa. Or 'in the pipeline! The crude ethanol product can be separated from hydrogen and/or other non-condensable gases (n〇n_c〇ndensablegases) by one or more separation membranes. The vapor stream 1M may contain Wei and hydrocarbons, which may be blown, purged, and/or returned to the reaction zone. As shown, the vapor stream is combined with nitrogen and co-sprayed. In some real-life formulas, the return-vapor stream 114 can be compressed prior to combining the hydrogen feed 104. The liquid stream 113 from the separator 106 is pumped and sent to the first distillation column 1〇7, which is also referred to as " 'Extractive steaming scales. The heatable liquid stream 113 can be heated from ambient temperature to temperature up to thief, for example, up to 5 &lt; TC or 4 〇. 〇: Liquid stream (1) preheated above The additional energy required for 7 〇 γ, f does not reach the energy efficiency to be achieved by the load of the reboiler in the first steaming tower (10). In the other two embodiments, the liquid stream 113 is not additionally preheated, but Separated, and if necessary, at a temperature below 7 (rc, for example below 5 (rc, or below 4 〇 &lt; t, cooled, and sent directly to the first distillation column 1〇7 ^ 201247301 In the embodiment of the invention, the liquid 黯 113 is the same as the crude ethanol product A of the line 112 obtained from the backing towel, except that the composition has depleted hydrogen, carbon dioxide, broth and/or B. Burning 'health is removed for its separation (four) 6). Thus, liquid stream 113 can also be referred to as a 6SI crude product. Table 2 provides (iv) the composition of the flow of the 113. It should be understood that the liquid stream 113 may contain other components not listed in Table 2. Table 2: Feed composition of distillation column 107 (liquid stream 113) Concentration (% by weight, concentration (weight concentration (weight ethanol 5 to 72 10 to 70 15 to 65 acetic acid &lt; 90 5 to 80 0 to 35 water 5 to 40 5 to 30 10 to 26 ethyl acetate &lt; 30 1 to 25 3 to 20 acetaldehyde &lt; 10 0.001 to 3 0.1 to 3 acetal &lt; 5 0.01 to 5 0.01 to 3 acetone &lt; 5 0.0005 to 0.05 0.001 to 0.03 Preferably, the amount shown below (&lt;) in the entire application specification sheet is absent, if present, may be present in minor amounts, or above 0.0001% by weight. In one embodiment, in liquid stream 113 The ethyl acetate concentration can affect the load and size of the first distillation 4107 re-retenterator. Reducing the concentration of ethyl acetate can allow for a reduction in the load and size of the reboiler. In one embodiment, to reduce the concentration of ethyl acetate: a) The catalyst in the reactor can be converted to ethyl acetate in addition to acetic acid, (b) the catalyst can have a lower selectivity to ethyl acetate, and/or (c) the reactor feed, including the regrind Can contain less ethyl acetate. As shown, the liquid 113 is introduced into the upper portion of the first distillation column 107, for example, the upper half or the upper third. As shown, one or more extractants 115, such as described above, also enter the first distillation column 107, To help separate the ethanol from the water (and other ingredients). Preferably, the extractant 115' is recovered directly or indirectly from the first residue and, as indicated by the circle, optionally, 201247301 optionally adds scale _125. The extractor 15 is positioned above the feed point of 3. For example, the extractant 115 is introduced near the top of the first steaming tower and is weighed down until it reaches the re-rear. In the mode, the extraction fine can be increased from the ambient temperature to 7 (TC, for example, a temperature of up to 5 (rc, or high meaning. c. In another embodiment, the stroke agent 115 is not separately preheated, but as in the first丨_7_ indicates that it is removed from the other _ tower, if necessary, cooled to a temperature below 7 (TC, | column is lower than thief, or less than 4 generations, and directly sent to the first steaming tower 107. As shown in Figure 6, depending on the concentration of ethyl acetate in the acetic acid recycle stream 147, this stream can be introduced into the liquid feed to the 113 feed point. In addition, the extracting agent 115 may be added to the above-mentioned acetonitrile circulating stream 147. According to the first steaming tower 〇7, it is known; the ethyl acetate indifference, ethyl acetate circulating flow The feed point will vary from 147. The extractant 115 preferably comprises water that has been hydrated. As described herein, the extractant 115 can be obtained from a portion of the second residue. The extractant 115 can be a dilute acid stream. Containing up to 20% by weight of acetic acid, for example up to 1% by weight of acetic acid or up to 5% by weight of acetic acid. In an embodiment, the mass flow ratio of water in the extractant 115 to the liquid stupid (1) may range from G.G5:1 to 2: for example, 'from 0.07:1 to G.9: 1, or From Gl: 1 to 〇.7: !. Preferably, the mass flow rate of the extractant 115 is lower than the mass flow rate of the liquid stream 113. In one embodiment, the first distillation column 107 has 5 to 9 theoretical trays, for example, from 1 to 60 theoretical trays, or from ^ to 5 theoretical trays. The number of trays can vary, depending on the efficiency of the tray, which is usually from 〇5 to 〇.7, and the tray efficiency depends on the tray type. The tray can be a sieve tray, a fixed valve tray, a moving valve tray or any other suitable design known in the literature. In other embodiments, a structured packing and a random packing of ran (jom pacing) may be used. When the first distillation column 1〇7 is operated at 50 kPa, the line 16 The temperature of the discharged residue is preferably from 20 ° C to 100 ° C, for example, from 3 〇 to 9: to 9 (TC, or 4 (TC to 8 (TC) by removing ethanol, ethyl acetate, The residual stream of water and acetic acid, the bottom of the first distillation column 1〇7 can be maintained at a relatively low temperature, thereby providing an energy efficiency advantage. Under the operating pressure of 5 kPa, from 20 201247301 - the tube of the steaming tower 1G7 The temperature of the effluent discharged from the road 117 is preferably 1 (rc is fine. c, for example, 20 C to 70 C or 30 C to 6 (TC. The pressure range of the first steaming tower 1 〇 7 can be from 〇 j kPa) Up to 510 kPa, for example, from 丨 kPa to 475 kPa or from 丨 kPa to 375 kPa. In some embodiments, the first steaming tower 107 operating pressure may be less than 7 ,, for example less than 5 〇 kPa, or low = 20 kPa. Operating under vacuum, can reduce the load of the reboiler and the reflux ratio of the first steaming scale. However, 'reducing the first steaming hall The operating pressure of the column 1〇7 does not significantly affect the steaming chamber diameter. ° The extraction dose fed to the extraction column 1〇7 can be very different. For example, when the extractant 115 contains dilute acid water, water to ethanol The mass flow ratio of the crude product can be from 〇〇5: out: for example, 'from 0.07:1 to 0.9:1 or (U:β〇7: the crude ethanol in liquid stream 113 contains ethyl acetate, ethanol and Water. These compounds can form non-binary azeotropes and ternary azeotropes. For example, ternary total _ can have a point lower than its composition (four) point ' ffij other ternary (four) can have a boiling point between pure Between the seaweeds of the ingredients. In the embodiment where the extractant is used, most of the ethanol will be transferred to the first wipe of the tube 117. By the first steaming age 1G7 extractant, Promoting the separation of ethanol into the first residue of line 116, thereby increasing the yield of the first residue alcohol in line 116. In this manner 'ethanol, water, unreacted acetic acid, and other heavy components if present Will be from the Newstream 113 towel Na iB, preferably the continuous gryphon, as the first in the pipeline 116 The first vapor bar 107 also forms a first weir, which is removed via line U7 and can be condensed and refluxed at a reflux ratio, for example with a reflux ratio from 3(): i to i: 3Q, like It is refluxed from 10.1 to 1 · 10 or from 5.1 to 1: 5. The higher the mass to mass flow ratio of the organic feed (mass flow mtb) is allowed to be -__7 low Reflux ratio operation" preferably, the first-column in line 117 contains the majority of the weight of ethyl acetate from the liquid stream 113. In the embodiment, the first library in the pipeline 117 contains vinegar 21 201247301, and the concentration of the siemen vinegar is lower than that of the vinegar and the concentrated production of the water silk towel vinegar. 75% by weight * &amp; In some embodiments, the first product in line 117 also comprises ethanol. Ethanol Return Reactor 103 may require an increase in reactor capacity to maintain ethanol at the same level. For the purpose of = ethanol recovery, optionally, the first product of line 117 can be sent to the extractor, and the residual liquid can have a lower concentration of ethanol and recovered to reactor 1〇3. The first-de-sent and the first-residue of the face are provided in the lower part, and the other scorpions of other fine towers in Table 3 can also have the class 1 requirement. , but the miscellaneous _ language is explained as Table 3: steaming tower 1〇7 ethanol water acetic acid ethyl acetate acetaldehyde acetal &lt;25 0.1 to 20 &lt; 2 10 to 85 0.1 to 70 &lt; 3 〇 · 〇〇 1 to 20 1 to 15 &lt; 0.1 15 to 80 0.2 to 65 0.01 to 2 concentration (repeated 〇.〇1 to 15 2 to 10 &lt; 0.05 20 to 75 0.5 to 65 0.05 to 1.5 first residue acetic acid ethanol Ethyl acetate 0.1 to 50 20 to 85 10 to 75 0.005 to 30 0.5 to 40 25 to 80 15 to 70 0.03 to 25 1 to 30 30 to 75 20 to 65 0.08 to 1 22 201247301 In an embodiment of the present invention, Due to the formation of the binary azeotrope and the ternary azeotrope, the first vapor column 107 can be moved to the residual stream under most of the water, ethanol, and acetic acid, while only a small amount of ethanol and water are collected at the temperature of the distillate stream. The weight ratio of the water in the residue of the line 118 to the water in the column 119 can be higher than 丨: 丨, for example, higher than 2 : 丨. The weight ratio of ethanol in the E. serrata in the residue is higher than 1: 1, for example higher than 2: 1. 1. The amount of acetic acid in the first residue may vary, depending on The conversion rate of the reactor 1〇3. In one embodiment, if the conversion rate is high, for example, higher than 90%, the amount of acetic acid in the first residue may be less than 1 Gil:%, for example less than 5% by weight. Or 2% by weight 〇 In other embodiments, if the conversion is low, such as less than 90%, the amount of acetic acid in the first residue may be greater than 1% by weight. Preferred in line 117 The first precipitate is substantially free of acetic acid, for example, containing less than 1,000 ppm by weight 'less than 500 ppm by weight, or less than 100 ppm by weight of acetic acid. The distillate can be purged from the system or all Or a portion is recycled to reactor 1〇 3. In some embodiments, if the distillate comprises ethyl acetate and acetaldehyde, the distillate can be further separated into acetaldehyde, for example, in a distillation column (not shown). Stream and ethyl acetate flow. The ethyl acetate stream can also be hydrolyzed or reduced by hydrogen to reduce hydrogen to produce B. These streams can be returned to reactor 1〇3 or separated from system 100 as an additional product. Some species, such as acetals, can be decomposed in first distillation column 107, so the amount is very low, even in distillate or There is no detectable amount of acetal in the residue. Further, an equilibrium reaction between acetic acid/ethanol and ethyl acetate may occur after the crude ethanol product is discharged from the reactor 103. According to the degree of acetic acid in the crude ethanol product, this balance can be clearly indicated to the acetic acid. This balance can be adjusted by the residence time and/or temperature of the crude ethanol product. In one embodiment, the balance may facilitate esterification to produce ethyl acetate due to the composition in line 117. Although the esterification reaction, whether in the liquid phase or the gas phase, can consume ethanol, the S-deuteration reaction also reduces the amount of acetic acid that needs to be removed from the process. The ethyl acetate may be formed from the first distillation column 1〇7 or by the acetalization between the first steaming tower 107 and the second steaming tower 1〇8. The acetification reaction can be further promoted by the first residue in the -partial line u (the acetalization reactor can be a liquid phase or a gas phase reactor, medium. Preferably, the lion gas phase reactor converts some of the first residue into an intermediate vapor feed and introduces it into the second distillation column 108. As shown in the first circle, 'the time is ethanol, and the residue in the line 116 can enter. The step separation depends on the concentration of acetic acid and/or ethyl acetate. In most embodiments of the invention, the residue of line ι6 is directed to a second vapor column 108, which is also referred to as "acid evaporation. Acid, job can be in the first: steaming fine residue = acetic acid concentration is higher than !% by weight, for example, higher than 5% by weight, can be separated by acid. In some embodiments, if the acetic acid concentration is low, for example Below the weight%, the water separation column shown in the third circle can be used. In the first circle, the first residue of the line 116 is introduced into the second distillation column 1〇8, preferably introduced into the steam. The middle part of the hall tower 1G8, for example, the middle two-point or the middle third. The second steaming tower 108 The raw tubing contains a second residue of acetic acid and water, and the tubing 9 contains an ethanol second iron. In the embodiment, most of the weight of water and/or is fed to the second distillate 108 The second residue of acetic acid in line 118 is removed, for example, at least _%, preferably at least 8% by weight of water and/or acetic acid is removed in the second side. For example, if The acid concentration of the residue is higher than 5 〇 ppm by weight, for example, more than 〇1% by weight, more than 1% by weight, such as more than 5% by weight, an acid distillation column may be necessary. In one embodiment, The first residue of line 116 may be preheated prior to introduction into second distillation column 1 8 : the first residue in line 116 may be the residue of the second distillation column (10) or the second distillation f 108 The vapor is integrated as heat. In some embodiments, if ethyl acetate is present, esterification can be carried out in the gas phase (not shown), with the result that the first residue in the line ΐ6 is preheated to Forming an intermediate vapor feed. For the purposes of the present invention, when preheating, it is preferably less than 3G mole % in line 116 - _ is in the gas phase, for example, less than or less than 2 mol of Mohr-residue in the gas phase. More gas phase content causes an increase in energy consumption and a significant increase in the size of the second distillation column 1〇8. The acetic acid esterification of the first residue in line 116 increases the concentration of ethyl acetate, thereby increasing the size of the second distillation column 108 of 201224301 and increasing the load on the reboiler. Therefore, the control of acetic acid conversion depends on The initial concentration of ethyl acetate removed from the first distillation column 107. To maintain efficient separation, the concentration of ethyl acetate in the first residue fed to the feed line 116 of the second distillation column 1 8 is preferably less than 1,000. The ppm by weight, for example 'below 800 ppm by weight or less than 6 〇〇 ppm ppm °, operates the first distillation column 1〇8 to concentrate the ethanol from the first residue 丨16, so most of the ethanol is from the top of the column «. Therefore, the material of the second column 1 8 may have a low ethanol concentration, less than 5% by weight, such as less than 1% by weight, or less than 5% by weight. The concentration of ethanol can be lowered without significantly increasing the load of the reboiler or the size of the distillation column. Thus, in some embodiments, it is effective to reduce the concentration of ethanol in the residue to less than 5 ppm by weight, more preferably less than 25 ppm by weight. As described herein, the residue in the second distillation column 1〇8 can be treated, and the low concentration of ethanol allows the residue to be processed without generating other impurities. Although the temperature and pressure of the second distillation column 108 may vary, at atmospheric pressure, it is preferred that the temperature of the second residue in the line 118 is from ^(^ to 丨(9)乂, for example, from i〇yc To 15〇.〇 or from 11(rc^145»c. In one embodiment, the first residue of line 116 is preheated to 2 of the temperature of the second residue of line 118 (rc, for example, at ^乂 or (7)弋, within the range of the second distillate discharged from the line 119 of the second steaming tower 108, such as from 75mrc, or 8(rc[irc. in the second 108 The bottom temperature gradient can be sharper. The pressure of the second distillation column 108 can range from 0 j kPa to 51 kPa, for example, from 丨 kPa to 47 kPa, or from i kPa to 375 kPa. By way of example, the second steaming tower (10) is operated at a pressure above atmospheric pressure, for example, above 17 〇 kPa or above 375 kPa. The building material of the Guta 108 may be, for example, 316LSS, A··, or Fine load, depending on the operating pressure. The load of the (4) and the size of the second fine tower remain relatively stable until the ethanol concentration in the second hall of line 119 is higher than 9〇. %. ^文=The first steaming (four)1〇7' is preferred to extract steamed scales with water. The additional water is separated in the first steaming scale 108. Although water is used as the extractant, the first steaming can be reduced. 7 of the reboiler's load, but if the water machine is compensated (ie, the amount of money is 2, 2012, 2012, 301, 0.65, 1, for example, 'Nan Yu 〇6: j or higher than 〇54: i, it will cause the first The steaming scale (10) refills the load of the full vessel and counteracts any benefit from the first distillation column 1 〇 7. The second distillation column 108 also forms an overhead which is removed via line 118 and can be condensed. And reflux, for example, a reflux ratio from 12:i to i:12, for example, from 1〇: i to i: / or from 8 · 1 to 1: 8. Preferably, the top of the line 119 contains Percentage by weight, for example, 87 to 90% by weight of ethanol, the balance is water and ethyl acetate. The typical composition of the second steaming 1G8_seeds and residues is provided in the table below. It should be understood The residue and the residue may also contain other components not listed in Table 4. Table 4: Acid distillation column 1〇8 (Fig. 1) Second distillate ethanol ethyl acetate acetaldehyde water 70 to 99.9 &lt;10 &lt;5 0.1 to 30 Shanghai (% by weight) 75 to 98 0.001 to 5 0.001 to 1 1 to 25 Concentration (% by weight) 80 to 95 0.01 to 3 0.005 to 0.5 5 to 20 Second residue Acetic acid ethyl acetate ethyl alcohol 0.1 to 45 45 to 1 〇〇 &lt; 2 &lt; 5 0.2 to 40 55 to 99.8 &lt; 1 0.001 5. S 0.5 to 35 65 to 99.5 &lt; 0.5 &lt; 2 Cao Jinzhong second touch The ethanol is in the second residue of the ethanol in the line 118. In the embodiment, the weight ratio of water in the water in the second residue (10) 118 is higher than 2:1, for example, higher than 1 2 : 1, or higher than 6: 1. = is the acetic acid in the second residue 118 to the acetic acid 26 1 1 ' of the second touch in the line ι9, for example above 15 · 1 ' or higher than 20: 1. Preferably, the conduit (10) 2, - substantially * contains acetic acid, if any, may contain only traces of acetic acid. 201247301 The decrease in acid concentration is conducive to the supply of no acetic acid content or the second _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Pipeline = In the figure of ^1, for the recovery of water as a second residue in the first steaming tower 丨 = two residues into the aqueous stream and the acetic acid stream, the second residue of the r pipe, however, As shown in Fig. 4: Dingqi = "green ϊ ϊΐ device, molecular sieve, or separation membrane, can also be used to separate the second (four) traits of the third lion in the pipeline 118, preferably Ϊ Ϊ steam Splash the top part of 4, such as the 'top half or the upper third. Preferably, in the line (2), water and very low acetic acid are contained, the content of which is, for example, less than 5 weights, and the weight is lower than the weight. The third material in the line 121 can be returned to a distillation column 107 as Extractant 115, or if necessary, blown off. W f three 顾 Gu f1G9 can be a kind of tray steaming _ or filling steaming. In one embodiment, the third steaming 109 is tray-type steaming, which has 5 to 15 trays, such as 50 trays or 20 to 45 trays. Although the temperature and pressure of the third steaming tower 1〇9 may be the same as the third residue temperature discharged by the line 120 at atmospheric pressure, preferably from 115 C to 140 C 'eg 'from coffee (3) Order, or from 125. (3) Price. In the atmosphere, the temperature of the third hall discharged by the pipe m is preferably from 9〇e (^li(rc, for example, =5 C to 110 c ' or 10 CTC to litre 〇 third steaming tower (10) The pressure range can range from 千 kPa to 510 kPa, for example, from 丨 kPa to 475 kPa, or 丨 kPa to 375 kPa. In another embodiment, the acid steamed scale can also be manipulated to remove The second residue comprises acetic acid and the second material comprises ethanol and water, and the water can be recovered by separating the ethanol and the water. In the second figure, the second steaming tower 122 can be a tray type steaming tower or a filling type. In the embodiment, the second display is a tray-type steamer having from 5 to 5 trays, for example from 15 to 50 trays or from 20 to 45 trays. The temperature at which the gas m is operated at fresh atmospheric pressure' is then discharged from the line 123, preferably from, for example, 105. (: to 117. 〇 or from 11 (TC to 115. 〇 by the second The temperature of the distillate discharged from the steaming valve 122 line 124 is preferably from 7 (TC to 1 UTC, for example, from it to, or 8 (rc 27 201247301 to 90 ° C. In other embodiments) Second distillation The pressure range of 122 can range from 千1 kPa to 51 kPa, for example, from 1 kPa to 475 kPa, or 1 kPa to 375 kPa. The second distillation column 122 distillate is provided in Table 5 below. Typical composition of the residue. Table 5: Acid distillation column 122 (Fig. 2)

Distillate Ethanol Water Acetic Acid Acetic Acid Acetic Acid S! Acetaldehyde Residue Acetic Acid Water Ethanol 10 to 85 5 to 60 &lt; 2 &lt;0.5 &lt; 2 60 to 1 〇〇 &lt;30 &lt; 1 15 to 85 10 to 50 0.001 To 〇.5 &lt;0.01 &lt;0.01 20 to 85 10 to 45 〇·〇1 to 0,2 0·001 to 〇.〇1 〇·〇〇ΐ to 0.01 65 to 1〇〇〇.5 to 30 &lt ; 0.9 85 to 95 1 to 15 &lt; 0.07 The second residue in line 123 can be recycled back to the reaction zone ι〇ι, the water in the second residue 123, if any, consistent &amp; Force S Yifuaw — . Can be used as an extractant. Then, the residue: two right-residues contain a very small amount of acetic acid, for example, less than 5% by weight, and the organic matter contained in the product, such as acetic acid, can be micro-recorded. The residual water is continuously read as shown in Fig. 2, and the remaining water, if any, is removed from the second material of the line 124. The implementation of the reduction of the butterfly in the second hall of the road to some applications in addition to the example == = wide alcohol product can be obtained from the tube water and other fine, such as fuel applications, may need to use anhydrous ethanol. The use of several 28 201247301 different separation tests to remove water from line 124 (d) two corrections includes the use of steaming towers, separation membranes, adsorption units, and combinations thereof. Priority J is preferred. In the previous implementation of the mountain method, after the water is removed, the ethanol product can be recovered. As shown in Fig. 2, the second plant in the line 124 is sent to a third distillation 126, such as an ethanol product. The distillate becomes the third museum output (B_exit) in the pipeline (3), and the pipeline = a residue (water residue). The third residue in the line 127 or a portion thereof can be returned to 3 = age 107 as the extraction. According to the required amount of water as the extractant, the second residue in the line (2) can also be added to the gas in the tube. The second bottom of the road 124 is 'for example, the lower half or the lower third. In general, the pipe distillate is refluxed at a reflux ratio, for example, the reflux ratio is from 丨:1〇 to 1〇:丨, such as from broad, or from 12 to 2.1. The second steaming tower 126 is preferably a tray type steaming tower as described above, preferably operated at atmospheric pressure. The temperature is preferably from 6 〇 ° C to ll (Tc, for example, from 7 〇. (: to l 〇〇 ° C, or 75 ° C to 95) from the third distillation column (9). C. When the steaming tower is operated at atmospheric pressure, the third residue temperature in line 127 is preferably from 70 C to 115 ° C, for example 'from 8 〇. 〇: to lKTc, or 85 eC to 105 〇: The typical composition of the precursors and residues of the third steaming tower 126 is provided in Table 6 below. It should be understood that 'the exhibits and residues may also contain other ingredients not listed in the table. For example, the ingredients in the feed. 29 201247301 Table 6: Ethanol Product Distillation Column 126 Concentration (Heavy/詈〇) Concentration (% by weight) Concentration (Cao Jinyu/Λ Distillate Ethanol Water Acetate Acetate 75 to % &lt;12 &lt;1 &lt;5 80 to 96 1 to 9 0.001 to 0.1 0.001 to 4 phantom to 96 3 to 8 0.005 to 〇.〇1 0.01 to 3 Residue water ethanol ethyl acetate acetic acid 75 to 1 〇〇 &lt;0.8 &lt;1 &lt;2 80 to 100 0.001 to 0.5 0.001 to 0.5 0,001 to 0.5 9 to 1 to 0.005 to 〇.〇5 0.005 to 〇.2 0.005 to 〇, 2 in another In the mode t, it is preferred that the conversion rate of the acid in the reactor 103 is high, and a steaming tower can detect the ethanol product and use water as a solution to the top scarf, which will be the first residue in the pipeline. The second distillation column 129 is sent, which is called "dilute acid recovery refractory tower." The second steaming 129 of Fig. 3 operates in a manner similar to the second phenotype of the magical figure, and (4) large in addition to the residue. /7 of water. The water from the first residue in line 116 can be separated into a second residue in line 132 and returned to first steam column 107. There can be some second residues in line 132 The sour acid (also referred to as a dilute acid stream) may be added with a blow purge 133 if desired. In some embodiments, the dilute acid stream 132 may comprise at least 85% from the ethanol crude product 113, for example, at least 90% 'especially at least 99-touch acetic acid. In the meantime, the dilute acid stream 132 may optionally comprise 85% to 99.5% or 90% to 99.99% of unreacted vinegar I from the crude ethanol product. In some embodiments, the dilute acid stream 132 comprises from 2 to 6 wt% acetic acid and from 4 to 98 wt% water. In an embodiment, the second front of the conduit m Even if it contains acetic acid', it can be returned to the first vaporization deuteration 107. For example, the dilute acid stream 132 can contain less than 30% by weight, such as 'less than 15% by weight, less than 1% by weight, or less than 5 Weight % of acetic acid. 30 201247301 Broken with 2 1 Residue 132 (Fig. 3) In the presence of high concentrations of acetic acid, the water separator membrane county. The wealth _38 can be, for example, a mining device, a separate water/acid separator or a combination thereof. The pressure swing adsorption device can be used to permeable membranes from water of (4) acid. In Fig. 4, the first-residual column 134 of line H6 operates in a manner similar to the second steaming in Figure 1. The water and acid from the first residue can be separated into a second residue of the path (3) and fed to the 138. The second separator in the water separator 138 separation line 136 becomes in the line 3 = aqueous stream and in the tube acetic acid stream m mode, the aqueous stream may contain a small amount of acetic acid and may be referred to as a dilute acid stream. The aqueous stream may comprise acetic acid in an amount of less than 20% by weight, such as less than 15% by weight, less than 1% by weight, or less than 5% by weight. In some embodiments 'based on the amount of acid in the second residue 136, the second residue may be purged by blow-off in the pipeline to the reaction, or may be treated as discussed above. As shown in Figure 4, the aqueous stream 139 can be returned to the first vapor column 1〇7 as an extractant. There may be some tannic acid in the water, 139 in the tilting towel, and the secret 139 can be combined with fresh water 125 ’ and then returned to the first steaming tower 1〇7. The acetic acid stream (10) from the water separator 1; 38 preferably contains acetic acid at a still present concentration. The acetic acid stream 140 can be returned to the reaction zone 1〇1. In one embodiment, the acetic acid in the second residual stream from the acetic acid distillation column can be depleted by reaction, leaving a pure aqueous stream. In Fig. 5, the second residue 132 is directed to the third distillation column 141 for esterification. In one embodiment, substantially all of the unreacted acetic acid is depleted in the first residue 132. According to the present invention, acetic acid in the second residue 132 is reacted with methanol in the line 142 in the 5a unit 141 to produce methyl acetate in the line 143. Although methanol is used in the foregoing, it should be understood that other alcohols may be used, including mixtures of ethanol or alcohols. For example, if ethanol is used instead of methanol, ethyl acetate will be produced in line 143. As shown in Fig. 5, the esterification unit is a reactive distillation column (third distillation column) 141. The second residue 132 and the methanol stream 142 are fed to the third distillation column 141 to produce a third residual stream 145 comprising methyl acetate, and a third distillate stream comprising water. At least a portion of the third residual stream can be purged from the system by line 145. Figure 5 shows the methanol feed stream .142 fed to the third steaming tower 31. The location of 201247301 is sent to the second residue 132 below the third steaming tower point. In other embodiments, the methanol feed stream may be sent to the second vapor column 141 at the same level as or below the second residue feed point to the third vapor column. "If the third steaming tower 141 is a reactive steaming tower, as shown in Fig. 5, the third steaming tower 141 comprises an ion exchange tree, an acid catalyst, or a combination thereof. Examples of non-limiting ranges of medium ion exchange resins include OnaeoOpomus stroi^add eati〇n exchange resins) ' For example, those obtained from Dow Chemical Company (for example, _ _5® 'Amberlysm® and Amberlyst 36®.) 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, the entire disclosure of each of The acid is added to the third distillation column 141 to catalyze the esterification reaction. In this state, the acid may be selected from the group consisting of sulfuric acid 'phosphoric acid, sulfonic acid, heteropolyacids, other inorganic acids, and their A group of mixtures. In other embodiments, the acid catalyst comprises a zeolite and a support which is treated with a mineral acid and a heteropolyacid. In some embodiments, if an ion exchange resin is present The third distillation column 141, before being fed to the third distillation column 141, may be fed to a guard bed (not shown). In one embodiment, the guard bed comprises an ion exchange resin as disclosed above. Although not limited to any particular theory, the guard bed can remove one or more corrosive metals in the second residue 132, thereby minimizing any ion exchange resin catalysis of the exchange resin in the third distillation column 141. Purification of the sites The operating parameters of the third distillation column 141 can be modified to achieve the desired composition at the third distillate 143 and/or the residual stream 144. For example, in some embodiments, temperature, pressure, progress The feed rate and residence time can be varied to increase the conversion of the acetic acid ester to reduce the formation of impurities to achieve more efficient separation to reduce energy consumption, or a combination thereof. In one embodiment, the third distillation column 141 bottom operating temperature from 100. (: to 15 〇. (:, for example, from 100 ° C to 130 ° C, or from 10 (TC to 120 t. In terms of pressure, the reaction distillation column can be at atmospheric pressure, times Operating at subatmospheric pressure or superatmospheric pressure. 32 201247301 til application method, countering the pressure of scale operation, build a thousand handles from Caipa, for example, from 50 kPa to 400 kPa' or from 5 〇 From kilopascals to 2 kPa. In some embodiments, the acetic acid and alcohol feed rates of the third distillation scale 141 can be delivered to the molar ratio of the acid to alcohol of the third distillation scale 141. For example, In the second two modes, the molar ratio of acetic acid to methanol in the reaction tower is from i: 丨 to - for example 'from 1:1 to 1 · · 5, or from i : 1 ' the third steamed crane tower The residence time of 141 affects the conversion of acetic acid. For example, in one formula, the residence time in the third steaming tower is from i to 5 hours, for example, from hours, or less than one hour. The third take-off product discharged from the third distillation column 141 in the line 143 is preferably 1-5%, which is preferably 5% by weight, and preferably the red is less than the weight of the wei, or the best To v65 wt% of acetic acid, the third substance 143 from the third steaming secret (4) can be known to 99% by weight, for example, % to _% by weight, sensitive to 5 parts by weight of acetic acid A cool. If excess sterol is reacted with acetic acid from the dilute acid stream, some methanol may also be present in the third effluent 143. Therefore, the third library outlet 143 may contain sterols from 〇% by weight, for example, from 1 至 to 60% by weight, or from 1 to 3% by weight. During the reaction of the second distillation column 129, some impurities such as dimethyl ether may be formed. In the second distillate stream 143, the content of these impurities can be very low, even without the amount detected. In some embodiments, the third distillate 143 comprises less than 1, 〇〇〇 by weight ppm, for example, less than 750 ppm by weight, or less than 5% by weight of dimethyl ether. The second library outlet stream 143 can be fed to a basement reactor for the production of acetic acid, which in turn can be used as a feedstock for the ethanol synthesis reaction. In some embodiments, the third distillate stream 143 can be optionally condensed, processed, or refined prior to being fed to the carbonylation reactor. In one embodiment, an additional third distillation column 146 can be used due to the presence of ethyl acetate in the second distillate 131. A third distillation column 146, also referred to as a "light fraction distillation column," is used to remove ethyl acetate from the second distillate 131, and a third residue in line 148 is used to make B 33 201247301 alcohol product. The light museum steam tower M6 can be a tray type steam tower or a filled steam tower tower 6th, and the third steam tower 146 can have 5 to 9 theoretical trays, for example, 1 to ^ Tray, or 15 to 50 theoretical trays. The feeding position of the second museum's 131 may vary, depending on the concentration of ethyl acetate, and the second is the second. The upper part of the yam tower is exhausted. The high concentration of acetic acid & is intended to feed into the higher position of the third steaming valve 146. The position of the feed should be avoided at the very top of the tray 'close to the reflux to avoid _ tower again (four) too much The load and the tower's stipulations are required. For example, in a steaming tower with 45 actual trays, the position of the feed should be between the 10th and the 1stth of the trays. The above point feeds and the size of the light shop steamed Na 146. h force Α ( (four) negative one second proud product 131 can feed the temperature up to 7 (rc, for example, up to order or 4 〇 two steaming In some embodiments, it is not necessary to preheat the second shaft (3). The acetic acid B is intended to be concentrated in the third take-up of line 147. Due to the relatively low amount of ethyl acetate Feeding the third steaming mash (10), the third crane product of the pipeline 147 also contains a large amount of recovered ethanol. The third museum output in the pipeline 147 can be fed into the first steaming tower 1〇7, which is lightly acid. 2 vinegar circulation flow. Because this will increase the first steaming tower (10) and the best one is in the tube fine (four) three postal money · ship's position _ quantity%: seeking from $ to 88% by weight, or from 75 to 85% by weight From 2 in other embodiments, the third portion of the portion in line 147 can be purged from the blow as another product, such as an ethyl acetate solvent. In an alternative embodiment, the third residue 148 It can be further processed to recover the required amount of water and ethanol. For example, it is necessary to inspect the tower and adsorb the U. If necessary, the water can be removed from the third residue of the tube coffee. In the process of entering the third distillation column 146, the water is firstly used to feed the ethanol into the step. The water is first removed from the vein, so that the third steaming scale is not required. The preferred one is operated under the slit steam pressure as described above. The temperature of the third residue from the first steaming and tearing line 148 is preferably ^ 34 201247301 from 65 ° C to 110 ° C, for example, from 7 (T (^10(rc, or 沱 to (10)乂. The temperature of the third donor discharged from the line 147 of the column 146 is preferably from 3 (rc to 7 〇 &lt;&gt;c ', 40 ° C to 65 ° C, or 50 ° C to 65 ° C. The pressure of the third distillation column 146 may range from 0.1 kPa to 510 kPa, for example, from 千 kPa to 475 kPa, or 丨 kPa to 375 kPa. In some embodiments, the third steaming tower (4) can be operated at a pressure below 70 kPa, such as below 5 kPa, or below 2 kPa. The operating pressure drop will substantially reduce the load on the column and the third column 146. The typical composition of the residue of the ethanol mixed stream and the third distillation column 146 is provided in Table 7 below. It should be understood that the exhibits and residues may also contain other ingredients not listed in Table 7. Knife concentration (% by weight) Concentration (% by weight) Concentration Γ Cao Jin%, 70 to 99 72 to 90 Μ to 85 0.5 to 30 1 to 25 1 to 15 &lt; 15 0.001 to 10 0.1 to 5 &lt; 10 0.001 to 2 〇.〇1 to 1 &lt;2 0.001 to 1 〇.〇1 to 0_5 80 to 99.5 85 to 97 90 to 95 &lt;8 0.001 to 3 0.01 to 1 &lt;1.5 0.0001 to 1 0.001 to 0.5 ^0.5 &lt;0.01 0.0001 to 0.01 Third distillate Ethyl acetate Acetate acetaldehyde Water acetal Third residue Ethyl alcohol ethyl acetate acetic acid 148. In some embodiments, water may be present in the 131 distillate, which may be transferred to the ethanol product stream in a mode prior to recovering the ethanol product prior to removal of the water. In one embodiment, the distillate in line 131 may comprise less than L5 wt% water, such as less than 10 wt% 35 201247301% water or less than 8 wt% water. The distillate in line 131 can be fed to a water separator, which can be an adsorption unit, a separation membrane, a molecular sieve, an extractive distillation column, or a combination thereof. In one embodiment, at least 50% of the second saturated material of line 131 is condensed and can be directed to third retort 146. One to Fig. 7 are diagrams showing the combination of the use of the reactive distillation column M1 and the ethanol product distillation column 146. In this schematic diagram, the second distillate 131 is fed to the ethanol product distillation column 146, and the second residue 132 is fed to the reactive distillation column 14 as a result of the purified ethanol recovery as a second residue in line 148, while acetic acid The ethyl ester is recovered as the third distillate 147 and sent back to the first distillation column 107. The second residue 132 is sent to the reactive distillation column 141, and the acetic acid and the methanol in the second residue are reacted to generate a subsequent gg, which is then in the line 143. The aqueous stream 144 is recovered as a fourth residue&apos; and the first item is returned as a scale. At least a portion of the aqueous 144 can be purged from the system by blowing in the line 145. Returning to the first strip of line 117, which comprises ethyl acetate and/or ethyl acetate, preferably refluxed at a reflux ratio as shown in Figure 1, for example, the reflux ratio from i: 3〇 to 3〇: Bu Ru, from 1: 5 to 5: Bud: 3 to 3: Bu is in the same state, not shown here, the No. Hall or its part can be returned to the reactor Yang. In some embodiments, the paste is a portion of the first-out-return reactor trace from the first-case acetic acid ethyl acetate and/or the reaction can be advanced in the hydrogenation reactor (10) or the second reactor reaction. . The effluent from the second reactor can be sent to the reaction H1G3' to produce more ethanol, or sent to a steaming tower to recover additional ethanol. In some embodiments, the first take-up at line 117 may further comprise a small amount of water. If all or part of the first touch is returned to reaction (4) 3, then it must be removed from line ι 7 such as 'the water from the first residue in line 117 can be removed by the adsorption device, one or more , molecular sieve, extraction steam tower or a combination thereof is removed. For example, the adsorption unit =) can be used to discharge the aqueous stream from the first column of the conduit 117 to produce a stream of intermediate components, preferably containing less than 1% by weight of water, and more preferably less than 0.5. The weight absorbing device can remove up to 99 water from the first faucet in line 117 to remove 95% to 99 99% of the water from the first item. The refined light component can be returned to the reactor 1〇3. 1 36 201247301 In one embodiment, one or both of the first distillate or a portion of the stream in line 117 is complete. The hydrazine can be further separated to produce a stream containing ethylene and a stream containing acetic acid. This allows a portion of the stream containing or containing the ethyl acetate stream to be recovered to reactor 1〇3 while blowing to purge other streams. Blowing off the stream can be used as a valuable source of ethyl acetate and/or acetaldehyde. The distillation column used in the present invention may comprise any distillation column capable of performing the desired separation and/or purification. Preferably, the distillation column comprises a tray distillation column having from 丨 to 〖% of trays, for example, from 20 to 95 trays, or from 30 to 75 trays, from 1 to ι00 towers plate. The trays can be sieve trays, solid (four) trays, transfer trays or any other suitable design known in the literature. In other embodiments, a filled steam can be used. As far as the filled steaming tower is concerned, the regular material, the material and the loose packing can be used. These trays or (iv) may be arranged in a continuous distillation column, or may be arranged in two or a seat, so that the liquid enters the second stage from the first stage and the liquid enters the first stage from the second stage. The associated condenser and liquid separation tank associated with each steaming can be any conventionally designed for use in a towel. Heat can be supplied to each bottom of the steam, or the bottom stream can be circulated through or _(rebc)ilel0° can also be used with other types of refills such as internal reboilers. The heat input into /, f 5 can come to the heat generated in the previous process, the process can be combined with the reboiler 2-= with the fourth (four) heat source, such as other heating chemical process or boiler. Although flash towers are shown as shown in the drawings, additional components, condensers, heaters 70 and other components may be used in various embodiments of the invention. The familiar art valve in this field can be combined and integrated in various condensers, pumps, compressors, reboilers, drums, process separation vessels, etc. of the 55 chemical process. The temperature and pressure of Lin can vary. Regardless of the temperature of the domain (10), the composition of the material at the position and the smelting of the smelting tester may be different. The rate of the feed may vary depending on the scale of the process. In general, the feed weight ratio can be between the technical field and the boiling point of the removed residue composition. For the general knowledge of the distillation, it is known that the temperature at the point of operation of the distillation column is 3737 201247301 in the tube. The cranes of roads 119, 128, and 131 contain ethanol, as described above, by means of additional = off-system, such as 'steaming (eg, towering towers), pressure swing adsorption systems, and alcohol production: The sieves s, 1 take the distillation column' or a combination thereof, and can be further purified 'to form an anhydrous ethanol product; IL, that is, the completed anhydrous ethanol". Any compound that passes through the fine process should be kept at a weight of B. ii. ί. ο.1% by weight 'for example, less than 0.05% by weight ' or less than 〇.〇2 ft. The percentage is ethanol. In terms of the total weight of the composition. In an embodiment, the impurities of any of the steaming towers are removed from the second steam. Preferably, it is used to remove the filament f. This f can be added _ _ and / or retained (d) The final ethanol composition obtained in the process of the invention of i can be taken out via the peak of the line U9, 131 or 135 - or optionally via the concentration of 8 residual components 帚Ethanol 85 to 99.9 water &lt;8 acetic acid &lt;1 ethyl acetate &lt;2 acetal &lt; 0.05 propylene &lt; 0.05 isopropyl alcohol &lt; 0.5 n-propanol &lt; 0.5 . concentration (% by weight) 90 to 99.5 0.1 To &lt;0.1 &lt;0.5 &lt;0.01 &lt;0.01 &lt;0.1 &lt;0.1 concentration (weight·§·%) 92 to 99.5 0.1 to &lt;0.01 &lt;0.05 &lt; 0.005 &lt;0.005 &lt;0,05 &lt;;0.05 alcohol. In the case of a real = 3 such as a f, n-butanol, isobutanol, isoamyl alcohol, etc., the isopropanol content in the finished ethanol composition is from (10) to ... (10) weighs 38 201247301 ppm 'For example' from 95 to 1, 〇〇〇 weight ppm, from lion to γ ό ο ppm by weight, or from 丨 5 〇 to 500 ppm by weight. In one embodiment, the finished ethanol composition is preferably substantially free of acetic acid and may comprise less than 8 ppm by weight acetaldehyde, such as less than 5 weight acetaldehyde or less than hydrazine ppm. The ethanol compositions completed in accordance with embodiments of the present invention are suitable for use in a variety of applications, including fuels, solvents, chemical materials, pharmaceuticals, detergents, disinfectants, hydrogenated delivery or consumer products. In fuel applications, denatured ethanol compositions can be blended with gasoline for use in motor vehicles such as cars, boats and small plug-in machines. In the non-fuel, the finished ethanol composition can be used as a solvent, a detergent, a disinfectant, a paint, an ink, and a drug for cosmetic and cosmetic preparations. The finished ethanol composition can also be used as a process solvent for pharmaceutical products, food preparations, dyes, photochemicals, and latex processing. The completed ethanol composition can also be used as a chemical raw material to make other chemical materials such as vinegar, ethyl acetoacetate, ethyl acetate, ethylene glycol, ethylene glycol oxime, ethylamine, lysine, high carbon alcohol, especially It is butanol. The ethylene compound which is produced in the production of acetic acid can be vinegared by (iv) acid. In another application, the finished ethanol composition can be dehydrated to produce ethylene. [Embodiment] In order to make the disclosure of the present invention more understandable, the following embodiments are provided. It should be understood that these examples are for purposes of illustration only and should not be construed as a limitation. EXAMPLES Eight kinds of separation processes of the present invention. The crude ethanol product was fed into the system containing three steaming towers. The first steaming operation was carried out using water as the extractant, and the extraction was not carried out: the vapor phase I was also tested under atmospheric pressure and a vacuum of about 33 kPa. The pressure demand and ethanol yield of the first steaming tower are disclosed in Table 9. 39 201247301 No water, _ __ Atmospheric pressure energy demand 1.66 [million British thermal units / ton of ethanol] Back to 87.1 〇 / 〇 ethanol in the residue Table 9 No water vacuum 0.68 7jC, water extraction vacuum 0,75 0.53 90.1% 98.3% 99.3% As shown in Table 9, when water is used as the extractant of the first-fine column, the number of _ towers drops to 0'75. At the same time, the amount of ethanol recovered rose from 87 1% to 98 3 II. The anvil was used as a steaming tower. 0 &amp; outside the pressure of the operation, although he has invented the details of the bribe, but it is obvious to those skilled in the art of this genre. The above discussion &amp; the present invention, the aspects and the various parts of the various embodiments and/or the various features and/or the following may be combined or interchanged in whole or in part. Various implementations in front! : Appropriately combined with other implementations, familiar with the field of technology = 2 =, which can be incorporated herein by reference. =: Yes; == The technical person understands that the foregoing description is only a [round simple description]. The invention is explained in detail below with reference to the various drawings, wherein like numerals refer to the same elements. Figure 1 shows a schematic diagram of an ethanol production system according to the present invention - an extractive distillation column for recovering extractant from acetic acid. Figure 2 is a schematic view showing an ethanol production system according to the present invention, which is a distillation column for recovering an extractant from ethanol. The third circle shows a schematic diagram of an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering a dilute acid stream of 201247301, and the dilute acid stream is suitable as an extractant. Figure 4 is a schematic view showing an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering an extractant, and is separated into acetic acid returned to the reactor by one or more water separation devices, and recovers water as an extractant. . Fig. 5 is a view showing an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering an extractant, and an esterification unit. Fig. 6 is a view showing an ethanol production system according to an embodiment of the present invention, which comprises a steaming tower for recovering a dilute acid stream, and another steaming tower for separating ethyl acetate and ethanol. Fig. 7 is a view similar to Fig. 6 in which an ethanol production system according to an embodiment of the present invention has an esterification unit. [Main component symbol description] Code description 100 Hydrogenation system 101 Reaction zone 102 Separation zone 103 Reactor 104 Hydrogen feed line/line/hydrogen feed 105 Acetic acid feed line/line 106 Separator 107 First distillation column /Extractive distillation column 108 First steaming tower / acid steaming tower 109 Third distillation tower 110 Evaporator 111 Pipeline *------------------ 41 201247301 Code description 112 Line 113 Liquid stream / ethanol crude product 114 vapor stream 115 extractant 117 line 118 second residue / line 119 second distillate 120 line / third residual stream 121 line 122 second distillation column 123 tube Road 124 Line 125 Fresh Water 126 Third Distillation Column 127 Line / Third Residual Stream 128 Line 129 Second Distillation Column / Dilute Acid Recovery Distillation Column 131 Second Distillate / Line 132 Pipeline / Dilute Acid Stream /Second residue 133 Blowing purge 134 Second distillation column 135 Line 136 Line 137 Line 42 201247301 Code description 138 Water separator 139 Line 140 Line / acetic acid stream 141 Third distillation column / esterification unit / Reactive distillation column 142 pipe / methanol Stream 143 Line / Third Distillate Stream 144 Third Residue Stream 145 Line / Third Residue Stream 146 Additional Third Distillation Column / Light Fraction Distillation Column 147 Pipe / Ethyl Acetate Recycling Stream 148 Pipe / Ethanol Product stream / third residue stream 43

Claims (1)

201247301 Seven patent application scope: 1. A process for producing ethanol, comprising: acetic acid in the acid feed stream to form a crude ethanol product; the crude product is in the presence of one or more extracting agents, separating at least part of the ethanol Vinegar and - species: the first splash of acid and ethyl acetate, and the first residue containing ethanol, acetic acid or Ethyl extractant; vinegar: B at least - part of the first residue - resulting in the inclusion of ethanol And a library of 'and a second residue containing one or more extractants; produced by the product 'containing acetic acid _ third German exports' 2. two = profit range! In the process described, wherein one or more extracting agents are selected from the group consisting of water, 1,4-butane, glycerol, diethylene glycol, 1 naphthalene 22, p-phenylene, N, N'-dimethyl Formamide, alcohol-tetrazide, glycol-1,5-pentanediol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol-propylenedipropene-tetrahydrobutanol, diethyl ether, methyl formate, Cyclohexene, N,N'-dimethyl-1,3-alkyl succinylethylenediamine, diethylenetriamine, hexamethylenediamine, diamine oxime, group! 7. The process described in the 12th, 13th, and 10th ton 'chlorination codes, and their mixtures>> the scope of application of the patent application, wherein a 4th f-type stroke agent is recovered in the second residue. And returned to the first distillation column. (2) The process described in the scope of the patent, wherein at least part of the second residue 5 is fined to the first-thousand tower, as one or more extractants β •= the process described in any one of the patent claims, Wherein the second residue returns 6 L 3 of less than 3% by weight of acetic acid. The invention described in the scope of the patent, wherein the first residue comprises less than 5 liters of ethyl acetate. The process described in any one of the patent scopes, wherein one of the one or more extractants at least 201247301 is produced together in the reactor. In the process described in the patent, the method of the invention is that the ethanol of at least the crude ethanol product is pumped to the first residue stream. 9. The process of claim 1, wherein the first thief comprises from 1 to 2% by weight of ethanol and from ! to 15% by weight of water. 10. The process of any of the preceding claims, further comprising separating at least a portion of the first residue&apos; to form an aqueous stream and a stream of acetic acid. 11. The process as described in the section above, further comprising returning at least a portion of the acetic acid stream to the reactor. 2. The process of claim 6, wherein the process of returning at least a portion of the aqueous stream to the first step is used as an extractant of one or more species. 13. The process of any of the preceding claims, further comprising reacting acetic acid from the second residue with at least one alcohol in the esterification unit to produce at least one ester and water; and separating at least from the water - Seeding produces a stream of product comprising at least one vinegar, and an aqueous stream comprising water. 14. The process of any of the preceding claims, further comprising returning at least a portion of the aqueous solution stream to the first vapor column as one or more extractants. 15. The process of any of the preceding claims, wherein the first distillation column is operated at a pressure of less than 7 kPa. 45