TW201245127A - Process to reduce ethanol recycled to hydrogenation reactor - Google Patents

Abstract

The present invention is directed to processes for recovering ethanol obtained from the hydrogenation of acetic acid. Acetic acid is hydrogenated in the presence of a catalyst in a hydrogenation reactor to form a crude ethanol product. The crude ethanol product is separated in one or more columns to recover ethanol. In some embodiments, less than 10 wt.% ethanol is recycled to the hydrogenation reactor.

Description

201245127 Code Description ^^ 127 Raffinate '130 Second Distillation Tower / Second 132 Second Distillate ^^ 133 Pipeline / Steam Tower Top 4^^ 134 Water Stream 135 Water Separator 136 Line 137 Line 138 Ethanol Mixture Stream 140 Product Column 141 Line ~ 142 Line ^ 150 Esterification Unit ~ 151 Alcohol Stream 152 Ester Product Stream 153 Column Substrate 154 Pipeline ^^ 5 If there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention. : VI. INSTRUCTIONS: CROSS-REFERENCE TO RELATED APPLICATIONS (Priority Claim) This application claims priority to US Patent Application No. 61/576,190, filed on Jan. 15, 2011. The disclosure is incorporated herein by reference. This 2012-24127 is also a part of the continuous application of US Patent No. 13/292,914, filed on September 9, 2011, and US Patent Application No. 13/094,588, filed on April 26, 2011. And the disclosure is incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a process for improving ethanol recovery using a distillation column, and more particularly to a process for reducing ethanol recycled to a hydrogenation reactor. [Prior Art] Industrial ethanol is prepared from organic sources such as petroleum, natural gas or coal, or from source intermediates such as syngas or from starchy materials or cellulosic materials such as corn or sugar cane. . Conventional methods for the production of ethanol from organic sources and from cellulosic materials include acid catalyzed hydration, methanol homologation (h〇m〇l〇gati〇n), direct alcohol synthesis, and Fischer-Tmpsch )synthesis. The unstable price of petrochemical sources will cause the price of ethanol produced by the law to fluctuate, making it more demanding alternative sources of ethanol manufacturing as the source price increases. Starch materials and cellulosic materials are converted to ethanol by fermentation. However, fermentation is generally used in the manufacture of consumer ethanol, and the ethanol produced therefrom is suitable for use as a fuel or for human consumption. In addition, fermentation of starchy or cellulosic materials competes with food sources and limits the amount of ethanol that can be made for industrial use. The production of ethanol via reduction reactions of saponins and/or other group-containing compounds has been extensively studied, and various combinations of catalysts, supports, and operating conditions have been described in the literature. In the case of reducing an alkanoic acid, for example, reducing acetic acid, other compounds may be formed together with ethanol or in a side reaction. These impurities limit the production and recovery of ethanol from this reaction mixture. For example, 'in the hydrogenation process' esters will be produced together with ethanol and/or water to form an azeotrope which will be difficult to separate. In addition, when the conversion is incomplete, the acid will remain in the crude ethanol product, which must be removed to recover the ethanol. EP 0 020 553 describes a process for the conversion of hydrocarbons to ethanol comprising the conversion of hydrocarbons to acetic acid and the hydrogenation of acetic acid to ethanol. The stream obtained from the hydrogenation reactor is separated to obtain a stream of ethanol' and a stream of acetic acid and acetic acid which will be recycled to the argonized 201245127 reactor. US Patent No. 7,842,844 describes a process for converting tobacco into ethanol in the presence of a particulate catalyst and reading it into an acetic acid towel as appropriate, and a process for improving the rotation and the quality of the product, which is via Syngas. An intermediate step is made. There is still a need for an improved process for recovering ethanol from a crude product such as a ferric acid such as an Anopheles mosquito or an aging compound thereof. SUMMARY OF THE INVENTION A first embodiment of the present invention relates to a process for producing ethanol, which comprises hydrogenating ethylene in the presence of a catalyst, and/or its purpose, and forming a residual stream; Separating a portion of the crude ethanol stream from a steaming tower to obtain a first distillate comprising (10), ethyl acetate and ethyl acetate, and a first residue comprising ethanol and ethyl acetate; in the second distillation column A portion of the first residue is separated to obtain a second residue comprising acetic acid and a second thief comprising ethanol and acetic acid; and recovering ethanol from the second arrogant. In some embodiments, the first residue further comprises a small amount of acetic acid. In one embodiment, the process includes separating at least a portion of the second library in the third vapor column to obtain a distillate comprising ethyl acetate and a third residue comprising ethanol. The first distillate is returned to the reactor and less than 10% ethanol from the crude ethanol stream, such as less than 5%, is returned to the reactor. In one embodiment, the first product is further separated to obtain an ethanol stream and a raffinate stream comprising ethyl acetate and less than 2% by weight ethanol. In other specific embodiments, the ethanol has a ratio of 14C:12C in acetic acid to the ratio of i4c:i2c in the living organism (^ to 丨. & first distillation column, the second distillation column And the total diameter of the third distillation column may be 5 to 4 mils, and further wherein the ratio of the first distillation column, the second distillation column, and the third distillation column relative to the total diameter per hour of ethanol produced The system is from 1:2 to 1:30. The second embodiment of the present invention relates to a process for producing ethanol, which comprises hydrogenating acetic acid and/or its ester in a reactor in the presence of a catalyst to form a crude ethanol liquid stream; Separating a portion of the crude ethanol stream from the first distillation column to obtain a first distillate comprising acetaldehyde, ethyl acetate and ethylene, wherein the first distillate has a flow from the crude ethanol stream Less than 10% ethanol, such as less than 5%; and first residue 201245127 comprising ethanol, acetic acid, ethyl acetate and water; wherein the first residue has at least 9% from the crude ethanol stream Ethanol, such as at least (four); separating a portion of the first residue in the second steam to obtain a second residue of acid and a second take-up comprising ethanol and acetic acid; and separating at least a portion of the second take-up in the third steaming tower to obtain a third comprising acetic acid (f); And a third residue comprising ethanol. The first, the product can be returned to the reactor. The third specific shot, the present invention is in the process of - difficult to make ethanol, including in the presence of a catalyst in the reactor Hydrogenating acetic acid and/or its vinegar to form a crude ethanol liquid stream; separating a portion of the crude ethanol liquid stream in the first distillation column to obtain a first-through product comprising acetaldehyde, ethyl acetate and ethanol and including The first residue of ethanol and acetic acid; the separated portion ^ the first library product has obtained an ethanol liquid stream and a raffinate stream comprising ethyl acetate, wherein the raffinate stream is returned to the reactor; The first residue of the separated portion in the distillation column is obtained to obtain a second residue comprising acetic acid and a second precursor comprising ethanol; and recovering ethanol from the second residue. In a specific example, the process may include Separating at least a portion of the second take-up from the third steaming tower to obtain In a fourth embodiment comprising ethyl acetate, and a fourth embodiment comprising ethanol, the invention relates to a process for producing ethanol comprising argonizing acetic acid and/or vinegar thereof in a reactor in the presence of a catalyst And forming a crude ethanol liquid to separate a portion of the crude ethanol liquid stream in the first distillation column to obtain a first distillate comprising acetaldehyde and ethyl acetate, and a first residue including ethanol, acetic acid and water Converting a portion of the third-residue to a portion of the vapor feed having less than 30 mole percent, preferably less than 25 mole percent of the vapor phase in the vapor phase; Separating the portion of the vapor feed to obtain a second residue comprising acetic acid and a second distillate comprising ethanol; recovering from the second take-up product; the first residue may be used as a secondary The reactor (s_da^ reactor) or the secondary vaporizer is converted into a partial vapor feed. In a specific example, the secondary reactor is a vapor phase esterification reactor. In the fifth specific example, the present invention is a process for producing ethanol, which includes in the presence of a catalyst The argonized acetic acid and/or its ester are formed in the reactor to form a crude ethanol liquid stream; the crude ethanol liquid stream is separated in the first steaming tower to obtain the first one including acetaldehyde, ethyl vinegar and ethanol. a distillate, and a first residue comprising ethanol, acetic acid, ethyl acetate, and water: 201245127 converting a portion of the first residue to less than 3 mole percent in the vapor phase, preferably a portion of the content of less than 25 mol%; the portion of the second portion of the second portion of the steam is fed with steam to obtain a second residue comprising acetic acid and a second comprising ethanol and ethyl acetate The museum produces; and recovers ethanol from the second museum. In one embodiment, the process can include the separation of at least a portion of the second material from the third fine towel to a third dish comprising ethyl acetate and a third residue comprising ethanol. The first museum output is returned to the reactor and less than 1 〇 0 / 〇 ethanol from the crude ethanol stream, such as less than 5% ethanol is returned to the reactor. In a specific example, the first product is further separated to obtain an ethanol liquid stream and a raffinate stream comprising ethyl acetate and less than 2% by weight of ethanol. In the sixth specific example, the present invention relates to a process for producing ethanol, which comprises providing a crude ethanol liquid stream; and separating a portion of the crude ethanol liquid stream in the first steaming step to obtain a copper brewing, acetic acid And the first residue of ethanol, and the first residue comprising ethanol and ethyl acetate; separating the portion of the first residue in the second steam to obtain a second residue comprising acetic acid and A second take-up comprising ethanol and ethyl acetate; and recovering ethanol from the second splash. In some embodiments, the first residue can include a small amount of acetic acid. And wherein the remainder comprises separating the at least a portion of the second remainder from the third basin to obtain a third derivative comprising ethyl acetate and a third residue comprising ethanol. The first feed is returned to the reverse yarn and less than the ethanol from the miscellaneous ethylene stream, such as less than 5% ethanol is returned to the reactor. In a specific example, the first precipitate is further separated to obtain an ethanol stream and a raffinate stream comprising ethyl acetate and less than 2% by weight of ethanol. Further, in the specific example, the ethanol has HC:12 of acetic acid (:_ is a ratio of Μ% to 5% of the living organism. The first distillation column, the second distillation column, and the third distillation column are The ratio of the total diameter of 5 to 40 meters and further wherein the ratio of the first steaming tower, the second steaming tower and the third steaming tower to the total tower diameter is small. : 2 to (4): The process may further comprise converting a portion of the first residue to less than 30 moles/min in the vapor phase; and 25 mol% of the content portion Steaming; separating a portion of the vapor feed from the second vapor column to obtain a second residue comprising acetic acid and a second distillate of ethanol; and recovering ethanol from the second distillate. 201245127 [Embodiment] The present invention relates to a process for recovering ethanol obtained by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction produces a crude ethanol liquid stream comprising ethanol, water, ethyl acetate, ethylene glycol, and other impurities. The process of the present invention comprises the step of separating the remaining ethanol stream of the first cap to include ethanol, water, acetic acid, and The acid residue stream and the liquid stream comprising (4) and ethyl acetate vinegar. The first column mainly shifts the light (4) machine of the waste towel and returns the organic matter for subsequent hydrogenation. Even if the residue is removed The main part of the ethanol in the liquid stream is used to obtain the ethanol product, but some (10) will be withdrawn and the miscellaneous materials will be recycled to the reactor. In a specific example, preferably less than 10 % of the ethanol from the crude ethanol stream is less than 5% or less than 1%, and returns to the reaction H ^ in the range table, and the amount of ethanol returned is the amount of ethanol in the crude ethanol stream. Up to 1%, such as from 5% to 5% or from 〇2 to 1%. In a specific example, in order to reduce the amount of ethanol recycled, the present invention operates the first column to remove more ethanol from the residue. This is operated with an extractant and/or pressure. In another embodiment, the distillate of the first residue can be extracted to extract ethanol and reduce the amount of ethanol recycled to the hydrogenation reactor. Ethanol, more ethanol will pass through the hydrogenation reactor, causing undesired loss of ethanol production Advantageously, this separation process results in a reduction in the energy required to recover ethanol from the crude ethanol stream, especially when recovering anhydrous ethanol for fuel grade ethanol. The process of the invention uses one or more distillations when recovering ethanol. In a preferred embodiment, in the initial column, for example, the residue stream in the first column comprises more ethanol than the distillate stream in the starting column. In some embodiments, The residue stream comprises a majority of ethanol, water, and acetic acid from the crude ethanol stream. When expressed in ranges, the residue stream can include from 50% to 99.9% ethanol from the crude ethanol product, such as 70%. Up to 99.9% or 90 to 99.5%. Preferably, the amount of ethanol from the crude ethanol product recovered from the residue is greater than 97.5%, such as greater than 99%. The residue stream comprising ethanol, ethyl acetate, water and acetic acid can be separated to recover ethanol. Since the compounds may be in an unbalanced state, additional ethyl acetate may be produced via esterification of ethanol with acetic acid. In a preferred embodiment, water and acetic acid may be used as another residue in another distillation column in 201245127. The liquid stream is removed. Further, the water carried through the other distillation column can be removed by a water separator selected from the group consisting of an adsorption unit, a helium, an extraction column, a molecular sieve, and combinations thereof. Although the ethyl acetate fraction is extracted into the first distillate, the higher concentration of acetic acid in the first residue causes an increase in the concentration of ethanol in the first residue and a decrease in the first inversion. Ethanol concentration. Therefore, the overall ethanol recovery rate can be increased. Depending on the concentration of ethyl acetate in the residue and depending on whether the residue or the acetation reactor is acetalized in situ, it may be necessary to further separate the ethyl acetate and ethanol in the separation column. Preferably, the separation column is located after the water has been removed using a distillation column and/or a water separator. Usually, when the residue comprises at least 50 ppm by weight of ethyl acetate, or there is in situ (the singularity may be reversed; the separation column may be necessary. When the ethyl acetate is less than 5 〇 weight, It is not necessary to use a separation column to separate ethyl acetate and ethanol. Ethyl acetate can be separated from the ethanol in the separation tray at the end of the purification process. The removal of the acetic acid can also remove the phase (IV) organic matter. The quality of the ethanol product can be improved by reducing the impurities. Preferably, the water and/or acetic acid can be removed before the separation of the ethyl alcohol. In the specific example, the ethyl acetate is returned to the ethanol and the ethyl acetate is returned. Until the initial tower towel is near the top of the scale, this allows any ethanol removed from the acetate to be reduced and thereby reduces the amount of ethanol recycled to the reactor. In some embodiments, ethanol is preferred. Recycling in the separation zone, but reducing the amount of re-alcohol. Decreasing the side ring to the reaction n of the _ can reduce the efficiency of the alcohol and the alcohol. Preferably, the removal of the first tower Acetic acid B is returned to the reactor with the purpose of the product. In the example, the residue of the first column comprises water and acetic acid from the portion of the crude ethanol stream. The residue stream comprises at least 8% water from the crude ethanol liquid and preferably at least 9G%. In the case of the brain, the residue preferably comprises from 100 to 100% of the water from the crude ethanol stream, and more preferably from 9% to the avalanche. The residue stream may comprise at least 85. % of acetic acid from the crude ethanol stream, for example at least 9% by weight and more preferably about 1%. The vane's precursor liquid may comprise from 8 to 100% of acetic acid from the crude ethanol stream. And more preferably (10)%. In a specific example 201245127, substantially all of the acetic acid is recovered in the residue stream. In a specific example, each distillation column is produced by capital and economically viable ethanol. The size of the manufacturing rate is determined by the size, and the total diameter of the steaming tower for separating the crude ethanol product may be 5 to 40 meters, for example, from 1G or from 12 to pr. Each fine column may have a varying size. - In the specific example, the steamed diameter of all bribes in meters is relative to the number of steam produced per hour. The ratio is from :3G, for example, from 3:1 to 2:2 or from 1.4 to 1·10. This will allow the process to achieve an hourly (four) ethanol production rate. The considerations include light organic matter such as acetic acid, diethyl condensate, ketone and acetic acid. In addition, trace amounts of ethanol and water may be present in the product. The initial steaming: removal of such light from the crude ethanol product The organic component provides an effective method for removing Ethyl acetate and ethyl acetate. In addition, when using a complex number of towers, (10), diethyl shrinkage and steel are not carried out with ethanol, thus reducing the self-- Ethyl secret and acetone by-product formation, in particular, acetic acid and / or acetic acid can be returned to the reactor and converted into additional ethanol. In another specific example, the exclusion gas is removed from the system Lightly the residue from the starting steaming tower comprises ethyl acetate. Although ethyl acetate is also partially found in the crane, the higher ethyl acetate concentration in the first residue will lead to an increase in the concentration of the first-residual ethanol and reduce the amount of the second in the first tower. Therefore, it can be added to the total The acetic acid (10) can be used in the separation column near the lining process, and the ethanol separation can also remove other light f organic substances and thus improve the ethanol product f by = low impurities. Preferably, water and/or acetic acid can be removed by separation of the acetic acid. In a specific example, after separating the ethyl acetate from ethanol, the acetic acid is returned to the top of the starting steamer. This makes the bottle of acetic acid B from the removal of any ethanol, and the amount of ethanol is low. The amount of ethanol in the reactor can be reduced. The amount of ethanol in the reactor can be reduced. , B ^ vinegar in the first - fine tower read the towel was removed and with (10) reward reactor. It can be used in B. The process of the invention can be used in any hydrogenation process for producing ethanol. The materials, catalysts, reaction conditions and separation processes in the hydrogenation using acid are detailed as follows: 201245127, the raw materials acetic acid and hydrogen used in the invention process can be touched. Any suitable source, including days,,,: gas / 生 from coal raw materials. For example, acetic acid can be produced by methanolization, acetic acid oxidation, oxidative oxidative fermentation, and anaerobic fermentation*. A process for the production of methanol suitable for the production of acetic acid is described in U.S. Patent No. 7,2,8,624; Incoming, 772; Naqiu; 6,657,〇78; 6,627'77〇, 6'143,93〇, 5,5",976 ; Μ 4'- ΙΟ%, woven, and ' 泽, and 4'994, 608 'the entire disclosures of which are incorporated herein by reference. Ethanol production can be integrated with the methanol carbonylation process, as appropriate. Since oil and natural gas prices are becoming more expensive or cheaper, methods for producing acetic acid and intermediates such as methanol and carbon monoxide from other carbon sources are gradually being accepted. In particular, when petroleum is relatively expensive, it is advantageous to produce acetic acid from a synthesis gas ('syngas,') derived from other available carbon sources. For example, U.S. Pat. No. 6,232,352, the entire disclosure of which is incorporated herein by reference in its entirety, is incorporated herein by reference. With the new methanol plant, the associated costs associated with the new acetic acid plant, and the accompanying problem of carbon monoxide generation, can be significantly reduced or substantially eliminated. All or part of the synthetic secret is derived from the methanol synthesis pathway and is supplied to the separator unit to recover carbon monoxide, which is then used to make acetic acid. In a similar manner, hydrogen from the hydrogenation step can be supplied from the syngas. In some embodiments, some or all of the feedstock of the above-described acetic acid hydrogenation process may be derived in part or in part from the syngas. For example, (10) can be formed from f alcohol and carbon monoxide, both derived from syngas. The synthesis gas may be formed by partial oxidation rearrangement or steam rearrangement, and the carbon monoxide may be separated from the synthesis gas. Similarly, the hydrogen used in the step of hydrogenating acetic acid to form a crude ethanol liquid stream may be separated from the synthesis gas. Can be derived from a variety of carbon sources. The carbon source may, for example, be selected from the group consisting of natural gas, gasoline, petroleum, biomass materials, or combinations thereof. Syngas or hydrogen can also be obtained from biologically derived hospital gases such as biomass-derived methane gas produced by waste burial or agricultural waste. Syngas derived from biomass material will have a detectable 14C isotope content compared to fossil fuels such as coal or natural gas. There is a balance between constant new formation and constant decay degradation in the Earth's atmosphere, and thus in the carbon nucleus of the Earth's atmosphere! The 4C ratio is long-term strange. Since the living organic system exists in the surrounding atmosphere, the HC:12C&s ratio of the same distribution ratio will be established in the living organism, and this distribution ratio will stop changing when the living organism dies, but the 14C will be about 6000. The half-life decay of the year decomposes. Syngas derived from the self-generating material, the methanol, acetic acid and/or ethanol fines formed will have a solid type and a binary body. For example, the %:% ratio of sterol, acetic acid and/or ethanol may be from one to a half of the ratio of C:1CC of living organisms to about 丨. In other specific examples, the syngas, methanol, acetic acid and/or ethanol described above are all derived from fossil fuels, that is, derived from 6〇, and the carbon source produced by the year before is not available. Detect the 14c content. In another embodiment, the acetic acid used in the hydrogenation step can be formed by fermentation from a biomass material. The fermenter produces fermented sugar into acetic acid and produces a very small amount, if any, of carbon dioxide as a by-product for the paste production process or the production of the beta organism. The carbon efficiency of the fermentation process is preferably greater than 7〇%, greater than 8〇〇/0 or greater than 9〇〇/0 compared to conventional yeast processes, which typically have a carbon efficiency of about 67%. As the case may be, the microorganism used in the fermentation process is a genus selected from the group consisting of Clostridium, Lactobacillus, M〇〇rella, and thermophilic anaerobic bacteria. Thermoanaerobacter, a group consisting of pr〇pi〇nibacterium, Propionispera, Anaerobiospirillum and Bacteriodes, and especially strains (Species) selected from Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Bulgarian lactic acid bacteria (Lact〇badllus) Delbrueckii), pr〇pi〇nibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum succinicproducens, Bacteriodes amylophilus and Bacteroides mminicola ) the group consisting of. Optionally, in the present process, the unfermented residue of all or part of the self-generating material (e.g., lignan) can be gasified to form hydrogen which can be used in the hydrogenation step of the present invention. An example of a fermentation process for the formation of acetic acid is described in U.S. Patent No. 6,509,180 and U.S. Patent Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are incorporated herein by reference. Examples of biomaterials include, without limitation, agricultural waste, forest products, turf and other cellulosic materials, wood residues in wood yards, cork sheets, hardwood chips, branches, trunks, -12· 201245127 leaves, bark, sawdust Specification pulp, corn, corn stalk, wheat crumb, rice crumb, bagasse, switchgrass, miscanthus, animal waste, municipal waste, municipal sewage, commercial waste, grape pumice, apricot shell, big walnut shell, coconut Shell, coffee grounds, grass, hay, wood, cardboard, paper, plastic and cloth. Other sources of biomass material are straw black liquor, which is an aqueous solution of lignin residues, hemicellulose, and inorganic chemicals. U.S. Reissue Patent No. RE35,377, which is incorporated herein by reference in its entirety, is hereby incorporated by reference in its entirety in its entirety in the the the the the the the the the The process involves hydrogenating a solid and/or liquid carbonaceous material to obtain a process gas that is cleaved with other natural gas vapor to form a syngas. The syngas is converted to methanol which can be further carbonylated to acetic acid. This method also produces hydrogen which can be used in the above invention. U.S. Patent No. 5,821,111 discloses a process for the conversion of waste biomass material to syngas via gasification, and U.S. Patent No. 6,685,754 discloses the production of a hydrogen-containing gas composition such as a synthesis gas comprising hydrogen and carbon monoxide. This article is for reference. The acetic acid fed to the deuteration reactor may also include other acid and acid species as well as acetic acid and acetone. Preferably, a suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic acid acetic acid, ethyl acetate, and mixtures thereof. These other compounds may also be hydrogenated in the process of the invention. In some specific examples, the presence of a tickic acid such as propionic acid or an aldehyde thereof may be advantageous in the manufacture of propanol. Water can also be present in the acetic acid feed. Alternatively, the acetic acid in vapor form can be obtained directly from the crude product in U.S. Pat. The crude steaming can be directly applied to the ethanol-supplied zone of the present invention without the need to condense or remove water from acetic acid and light hydrocarbons, thereby saving overall processing costs. The acetic acid can be vaporized at the reaction temperature, and then the vaporized acetic acid can be fed to the undiluted hydrogen or to a relatively inert carrier such as nitrogen, argon, helium, carbon dioxide or the like. The reaction in the vapor phase of the system, the temperature should be controlled so that it will not be lower than acetic acid. In a specific shot, acetic acid can be steamed under a specific pressure under acetic acid, and then the acetic acid vaporized by the lanthanum is further heated to the reactor inlet temperature: in another embodiment, the liquid is mixed with other gases before vaporization. Then, the mixture is steamed to be heated to the reaction H human D temperature. Preferably, the acetic acid is transferred to the vapor state by passing the hydrogen and/or lysine gas through the acetic acid at a temperature of •13-201245127 me or below 125 C, and then the combined gas stream is heated to the reactor inlet temperature. . Hydrogenated acetic acid and alkali B have some configurations of (4) fixed bed reactors or fluid bed reactors. In many embodiments of the invention, it is possible to use, insulate, and react, i.e., there is little or no need to introduce an internal t-channel reaction zone to add or remove heat. In his specific example, a radial flow reactor or reactors may be utilized, or a series reactor may be used, with or without charge, hot money, shafts or lead-in slides. Alternatively, a shell type and tubular type reaction crucible provided with fresh transfer medium can be used. In many cases, the reaction zone can be contained in a single-container or contained in a container having a heat exchanger therebetween. In a preferred embodiment, the catalyst is used in a fixed bed reactor, e.g., in a straight or tubular reactor, on or in the reactants of the vapor-like reactants. Other anti-offices such as fluids or manuscript beds can be used to react. In some cases, the hydrogenation catalyst can be inactivated by the inert material _ joint anti-mystery by contacting the bed with the contact time of the reactant compound with the catalyst particles. The hydrogenation reaction can be carried out in _ Silk. For the healthier, the anti-mystery is carried out in the vapor phase under the following conditions. The reaction temperature can range from INC to 35 〇t_^, such as from 2 〇 (rc to 325 t, from 2 pits to fine c, or from 25 (rc to · c. pressure can be in the attached bar (4)) to 3000 kbar. The range of (kPa) is, for example, from 5 〇 kPa (coffee) to 23 (8) kPa ((iv), or from (10) kPa (kPa) to 2 _ kPa (kPa). The reactants can be from 5 hours to Kunming Hour ·, gas hourly space velocity (GHSV) is fed to the reaction H, such as from hour i3W () hours, from 1,000 hours to 10,000 hours -1, or from !, _ hours · to 65 hours ·丨.

Although the reaction of each mole of acetic acid will be secreted by two moles of hydrogen to produce - molar ethanol, the actual molar ratio of hydrogen to acetic acid in the feed stream can be in the appointment (1): Qing to 1:50, from 2〇 :1 to 1:2, or from 18:1 to 2: Bu 5 (U contact or residence time can vary widely, depending on various variables such as amount of acetic acid, catalyst' reactor, temperature and pressure. When the bed is fixed, the time is from a few milliseconds to more than a few hours, and at least the reaction time to the vapor phase is from 0.1 to 100 seconds. According to 14 201245127 Hydrogenation of acetic acid to ethanol is preferred. In the presence of a hydrogenation catalyst, the catalysts are described in U.S. Patent Nos. 7,608,744 and 7,863,489, and U.S. Patent Publication Nos. 2010/0121114 and 2,10/Gl97985, the entire disclosure of which is incorporated herein by reference. The catalyst includes a c〇/M〇/s catalyst of the type described in US Publication No. 2009/0069609, which is incorporated herein by reference in its entirety. - In a specific example, the catalyst comprises a material selected from the group consisting of steel, iron, beginning, record, sputum, bond, Ji, hungry, bismuth, platinum, a first metal of the group consisting of zinc, chromium, lanthanum, molybdenum and tungsten. Preferably, the first metal is selected from the group consisting of starting, placing, recording, nickel and ruthenium. In some embodiments, the catalyst further comprises a second metal, which generally functions as a promoter. If a second metal is present, it is preferably selected from the group consisting of copper, turn, tin, chromium, iron, diamond, More preferably, the second metal is selected from the group consisting of copper, tin, record, chain, and record. The catalyst contains two or more types. In some specific examples of the metal such as the first metal and the second metal, the first metal is present in the catalyst in an amount of from 01 to 10% by weight, such as from 〇丨 to 5 重量/〇, or from 0.1 to 3 重量The amount of the second metal present is preferably 〇^2 〇 weight 0/., such as from 〇丄 to 10% by weight, or from 0.1 to 7.5% by weight. For example, the preferred metal composition of the catalyst composition comprises platinum/tin, platinum. /nail, platinum/chain, handle / ruthenium, palladium / rhodium, cobalt / handle, cobalt / turn, cobalt / chromium, cobalt / tantalum, cobalt / tin, silver / handle, copper / Ji, copper / zinc, nickel / Kim / Ji钌/铢, or 钌/铁. - The catalyst may also include a third metal selected from any of the metals listed in the above-mentioned first metal or second gold shot as long as the third metal is different from the first metal and the second metal In a preferred embodiment, the second metal is selected from the group consisting of cobalt, 35, antimony, copper, zinc, platinum, tin, and antimony. When the second metal is present, the total amount of the third metal is preferably As for, for example, % by weight, such as from 0.1 to 10% by weight, or from 0.1 to 7.5 % by weight, in particular, the catalyst may include turning, tin and cobalt. In addition to the metal or metals, some specific examples of the invention The catalyst further includes a support or a modified supp〇rt. The "reformer" used in this article does not include the support material and the support for the adjustment of the acidity of the support material. The total weight of the support tamper-retaining support is based on the total weight of the catalyst, preferably from 75 to 999% by weight, such as from %15.201245127 to 97% by weight or from 80 to 97.5% by weight. Preferred supports include tantalum supports such as oxidized oxide, cerium oxide/alumina, lanthanum cerates such as calcium metasilicate, pyrolytic cerium oxide, high purity oxidized cerium and mixtures thereof. Other supports may include, but are not limited to, iron oxide, aluminum oxide, titanium oxide, lead oxide, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbon, and mixtures thereof. The support may be a modified support and the amount of the support modifier present, based on the total weight of the catalyst, from 1 to 50% by weight, such as from 2 to 25 weights per liter. , from 1 to 2 〇 weight ❶ / ❶, from 3 to 15 weight. /. . In some embodiments, the bulk modifier may be an acid modifier that increases the acidity of the catalyst. Suitable acidic support modifiers may be selected from oxides of Group IVB metals, oxides of Group Vb metals, oxides of Group VIB metals, oxides of Vlffi metals, oxides of Group VInB metals, aluminum oxides and mixtures thereof The group consisting of the acidic carrier modifier comprises a material selected from Ti〇2

Zr02, Nb2〇5, Ta205, Ai203, B2〇3, p2〇5, Sb203, W03, Mo〇3, Fe203, 〇2〇3, V2〇5, Mn〇2, CuO, C〇2〇3 and Bi2 〇3 group of groups. Preferred Supports Modifiers include oxides of tungsten, molybdenum and vanadium. In another embodiment, the bulk modifier may be an alkaline modifier having low or no volatility. The alkaline modifier may, for example, be selected from the group consisting of alkaline earth metal oxides, (ii) alkali metal oxides (iii) soil-checking metal bismuth citrates, (iv) alkali metal bismuth phthalates, (ν) steroids. a group consisting of a metal oxide '(ν 金属 metal bismuth citrate, (νϋ) lanthanide metal oxide, (viii) InB group metal bismuth citrate and mixtures thereof. The alkaline carrier is modified The agent may be selected from the group consisting of oxides and metasilicates of any of sodium, potassium, magnesium, calcium, strontium, barium and zinc, and any of the foregoing oxides. In one embodiment, the test is modified. The agent is a sulphuric acid such as calcium sulphate (CaSi03). The bismuth citrate may be crystalline or amorphous. The catalyst on the modified support may comprise one or more selected from the group consisting of a ship, a handle, a drill, and the like. The metal of the tin and antimony group is supported on the cerium oxide support, and the cerium oxide support system has been selected from one or more modifiers selected from the group consisting of calcium metasilicate, and tungsten, molybdenum and/or vanadium oxide. The composition of the catalyst suitable for use in the present invention is preferably formed by metal impregnation in a modified support, but Other processes, such as chemical vapor deposition, are used. Such a saturation technique is described in the aforementioned U.S. Patent Nos. 7,6,8,744 and 7,863,489, and U.S. Publication No. 2010/0197485, the entire disclosure of which is incorporated herein by reference. After the completion of the burning, the catalyst can be reduced to activate the catalyst. Also - 16 - 201245127 The original system is also deposited in Wei Zaojia money. At the beginning of the touch Wenlang to Liu. c under the 'reduction gas continuously through the touch In one embodiment, it is preferred to carry out the reduction after the catalyst has been loaded on the reaction vessel to be hydrogenated. In particular, hydrogenation of acetic acid can achieve favorable acetic acid conversion, and favorable ethanol selectivity and Productivity. For the purposes of the present invention, "scaling" means the amount of acetic acid in the feed which is converted to a compound other than acetic acid. The conversion is expressed as a percentage of the acetic acid. The conversion can be at least Such as at least, at least (four), at least 80% or at least 80%. Miscellaneous with high conversion rate is more desirable, such as at least or at least 90% of the catalyst, but in some specific cases, high choice for ethanol Rate (four) coffee The low conversion rate catalyst is acceptable. The selectivity rate is expressed as the percentage of the molar amount of acetic acid that has been converted. It should be understood that the self-acetic acid conversion of the private compound has a lot of money, and the amount of God and the identification Independent of each other. For example, if 60 mol% of converted acetic acid is converted to ethanol, the conversion of ethanol is said to be 6〇%. Preferably, the selectivity to ethanol is at least 60%, such as at least 7〇%. , or ^ less 80 =. The preferred specific example of the hydrogenation process is not a low selectivity of the products of Lin, such as the low selectivity of broth, acetaminophen and carbon dioxide. The selectivity of these unanticipated products Preferably, it is less than 4%, such as less than 2% or less than 1〇/0. The term "productivity" is used to mean that the catalyst used per hour is heavier than the one formed during the ILization. The number of grams of product such as ethanol. The yield can range from (10) to 3, gram of ethanol per kg of catalyst per hour. In various embodiments of the invention, the crude ethanol product produced by the hydrogenation process generally comprises acetic acid, ethanol and water prior to any subsequent processing, such as purification and separation. An exemplary composition range for the crude ethanol product is shown in Table 1, except for hydrogen. The "others" indicated in Table 1 may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide. -17- 201245127 Crude ethanol product composition concentration concentration concentration % 量 %) (weight (% by weight) Component Ethanol Acetic Acid Water Ethyl Acetate Acetaldehyde Other Table Concentration (% by Weight) 5 to 72 0 to 90 5 to 40 〇 to 30 0 to 10 0.1 to 10 15 to 72 〇 to 50 5 to 30 1 to 25 〇 to 3 0.1 to 6 15 to 70 〇 to 35 10 to 30 3 to 20 0.1 to 3 0.1 to 4 - 25 to 65 0 to 15 10 to 26 5 to 18 0.2 5.2 - specific examples, the crude ethanol product of Table 1 may have a low A concentration of acetic acid, but a high conversion, and the acetic acid concentration may range from 0.1% by weight to 2% by weight, such as from 5% by weight to 15% by weight of 0.1'0.1% by weight to 10% by weight, or i weight. Up to 5 weights. In a specific case with a lower amount of acetic acid, the acetic acid conversion rate is preferably greater than 75%, such as greater than (four) or greater than 90 / 〇» In addition, the selectivity for ethanol is also higher. Preferably, it is higher, and preferably greater than 75%, such as greater than 85°/. or greater than 90〇/〇. Examples according to specific examples of the present invention The ethanol recovery system is shown in Figures 2 to 2. Each hydrogenation system 100 provides a suitable hydrogenation reactor for the specifics of the invention and a process for separating ethanol from the crude to the reaction mixture. System 100 includes reaction zone 101 and separation zone 1〇2, Other modifications and other components of reaction zone 1〇1 and reaction zone 102 are described below. In Figure i, additional extractor 120 and esterification unit 150 are shown. In Figure 2, secondary reactor 16〇 is shown and used. A portion of the first residue is converted to a vapor phase secondary vaporizer 161. As also shown in Figures 1 and 2, the feed to reactor 1〇3 includes fresh acetic acid. Hydrogen and acetic acid are fed via lines 105 and 106, respectively. Into the vaporizer 1〇4, and a steam feed stream is produced in line 1〇7, which is directed to the reactor 103. In a specific example, lines 1〇5 and 1〇6 can be combined and combined with the feed vaporizer 104. The steam feed stream temperature in 107 is preferably from 10 ° C to 350 ° C, such as from 120 ° C to 310 ° C or from 150 ° C to 30 (TC. Any steam that has not been steamed The material is removed from the vaporizer 1〇4 via the discharge pipe 108. Further, although the line 107 is shown as being introduced in the opposite direction At the top of the vessel 103, but the line 107 can be introduced into the side, upper or bottom of the reactor. • 18· 201245127 The reactor 103 contains a column of acetic acid hydrogenated with a better one. In a specific example, it can be upstream of the reactor ( Use one or more guard bedS (not shown), as appropriate, to protect the catalyst from contact with toxins or * contained in the feed or in the return/circulation stream. Impurity of being _. The gambling bed can be used in neonate or liquid streams. Suitable guard bed materials can include, for example, carbon, oxidized stone, oxidized, ceramic or resin. In one aspect, the guard bed media is functionalized, such as by silver, to capture specific species such as sulfur or halogen. During the hydrogenation process, the crude ethanol stream is withdrawn (preferably continuously withdrawn) from reactor 1〇3 via line 1〇9. The crude ethanol stream can be condensed and fed to a separator 11 which then forms a vapor stream 112 and a liquid stream 113. In some embodiments, the separator 11 can include a flasher or a Knockout pot. The separator no can be changed from the other, such as from 3cr (^325^ or from 60 C to 250 C. The pressure of the separator no can be self-excited (running) to 3000 kPa (kPa). ), such as from 125 kPa (kPa) to 2500 kPa (kPa) or from 150 kPa (kPa) to 2200 kPa (kPa). Optionally, the crude ethanol stream in line 1〇9 can pass through one or Multiple membranes to separate hydrogen and/or other non-condensable gases. The vapor stream 112 exiting the separator 110 can include hydrogen and hydrocarbons and can be purged and/or returned to the reaction zone 1〇1. As shown, steam stream 112 is combined with hydrogen feed 1〇5 and co-fed into vaporizer 104. In some embodiments, return steam stream 112 can be compressed prior to combination with hydrogen feed 1〇5. The liquid stream 113 is withdrawn and introduced into the side of the first distillation column 115 as a light hydrocarbon column, '. The liquid stream 113 can be heated from ambient temperature to a temperature of up to 7 ° C. Up to 50. 〇 or up to 4 〇〇 c. Preheating the liquid stream 113 to more than 7 〇 ° C requires additional energy in the first column 115 relative to the reboiler load, failing to achieve the desired In another embodiment, the liquid stream 113 is not additionally preheated, but is separated from the separator 110 and, if desired, below 70. (: if less than 50. (: or below 40. (: The temperature is cooled and fed directly into the first column 115. In a specific example, the contents of the 'liquid stream 113 are substantially similar to the crude ethanol stream obtained from the reactor' but the composition removes hydrogen, carbon dioxide, decane or Ethane, which has been removed by separator 110. Accordingly, liquid stream 113 may also be referred to as a crude ethanol stream. Example of liquid stream 113-19-201245127 The composition is found in Table h. It should be understood that liquid stream 1Π may contain The other components listed in Table 2. Table 2: Feed composition for column 115 (liquid stream 113) Concentration (weight ethanol 5 to 72 acetic acid < 90 water 5 to 40 ethyl acetate < 30 acetaldehyde < 10 acetal <5 acetone <5 concentration (% by weight) concentration (% by weight) 10 to 70 15 to 65 5 to 80 0 to 35 5 to 30 10 to 26 1 to 25 3 to 20 0.001 to 3 0.1 to 3 0.01 to 5 0.01 to 3 0.0005 to 〇.〇5 0.001 to 0.03 The towel of the entire specification is preferably the amount indicated by (<) Does not exist, or if present, 'is greater than 0.0001% by weight. In a specific example, the ethyl acetate concentration in liquid stream 1丨3 can affect the first column reboiler load and size. Reduce ethyl acetate concentration It can reduce the duty and size of the reboiler. In a specific example, in order to reduce the concentration of ethyl acetate, the catalyst in (a) the reactor will convert ethyl acetate in addition to acetic acid; (b) the catalyst is less selective to ethyl acetate, and/or (c) The feed to the reactor 'contains a cycle and may contain less ethyl acetate. In the specific example shown in Fig. 1, the liquid stream 113 is introduced into the upper portion of the first column 115, and in the above part 1/2 or 3/2, in addition to the liquid stream U3, the first column is fed with an optional extraction. The agent 116 and the ethyl acetate circulating liquid stream ip. Depending on the ethyl acetate concentration of the ethyl acetate recycle stream ip, this stream is introduced at a feed point above or near the liquid stream 113. It depends on the concentration of ethyl acetate in the first column 115. The feed point of the ethyl acetate recycle stream 117 is variable. Since the relatively high ethanol concentration of the ethyl acetate recycle stream 117 is from 70 to 90% by weight of ethanol as shown in Table 6 below, it is preferred to feed the ethyl acetate recycle stream 117 to the first column 115 instead of the reactor. 103. The liquid stream 113 and the ethyl acetate recycle stream 117 collectively comprise the organic feed of the first column 115 into 201245127. In one embodiment, the organic feed comprises hydrazine to 25% ethyl acetate recycle stream in, such as from 1% to 15% or from 1% to 1%. This amount may vary depending on the productivity of the reactor 1〇3 and the amount of ethyl acetate to be recycled. In some embodiments, the extractant 116 may be optionally disposed, preferably at a level above the liquid stream 113. The optional extractant 116 can be heated up to 7 Torr from ambient temperature. Temperature of 〇, such as up to 50 ° C or up to 40. (: In another embodiment, the extractant 116 is not preheated additionally 'but is drawn from the second column 130 and cooled to below 7 若 if necessary. For example less than 5 〇. 〇 or below 40° The temperature of C is fed directly into the first column 115. The optional extractant 116 preferably comprises water remaining in the system. As described herein, the extractant 116 can be obtained from a portion of the second residue. The agent 116 can be a dilute acid stream comprising up to 2% by weight of acetic acid, such as up to 10% by weight of acetic acid or up to 5% by weight of acetic acid. In one embodiment, the mass flow of water in the extractant 116 is relative to the liquid stream 113 and The ratio of the mass flow rate of the organic feed to the ethyl acetate recycle stream 117 can range from 0.05:1 to 2:1, such as from 0.07:1 to 0.9:1 or from 1:1 to 〇7:1. Preferably, the mass flow rate of the extractant 116 is less than the mass flow rate of the organic feed. In a specific example, the first column 115 has a theoretical plate number of 5 to 90, such as from 1 to 6 theoretical plates or The number of plates from 15 to 50 theoretical plates. The number of plates in each tower can be determined according to the efficiency of the plate. The efficiency of the plate is usually 〇5 to 〇 7. The plate may be a screen deck, a fixed valve plate, a movable valve plate or any other suitable design known in the art. In other embodiments, structured packing or random packing may be used. Packed Column* When the first column 115 is operated at 50 kilobars (kPa), the temperature of the residue flowing out of the line 118 is preferably from 20. (: to 100. (: ' as from 3 (TC to 90) °C or from 40. (: to 80 ° C. The base of the first column 115 is maintained at a relatively low temperature by extracting a residue stream comprising ethanol, ethyl acetate, water and acetic acid, thus providing an energy efficiency advantage. The temperature of the distillate flowing out of the first column 115 is preferably from 〇 0. 0 to 8 〇 at 0 〇 千 (kpa), such as from 2 〇 to 7 〇 C or from 30 ° C. Up to 60 ° C. The pressure of the first column 115 can range from 1 kilobar (kpa) to 51 kilobars (kPa), such as from kilobars (kPa) to 475 kilobars (kpa) or Thousands of bars (coffee) to 375 kilobars (kPa). In some specific examples, the first column 115 can be below 7 〇 kPa (kpa), such as less than % kPa (kPa) or less than 2 〇 kPa (kPa) operating in vacuum. In vacuum The operation can reduce the reboiling degree of the second column 115. However, reducing the operating pressure of the first column 115 does not substantially affect the column diameter. In the first column 115, the self-contained liquid stream The organic feed of 113 and ethyl acetate recycle stream 117 removes most of the weight of ethanol, water, acetic acid, and is withdrawn as a residue in line 118, preferably continuously. This includes any extraction as needed. The agent 116 is added with water. Concentration of ethanol in the residue will reduce the amount of ethanol recycled to the reactor 1〇3 and may therefore reduce the size of the reactor 103. Preferably, less than 1% by weight of ethanol is derived from the organic feed, such as from 5% or less of the ethanol being returned from the first column 115 to the reactor 1〇3. In addition, concentrated ethanol will also concentrate the water and/or acetic acid in the residue. In one embodiment, at least 90 〇/〇 ethanol from the organic feed is withdrawn from the residue and more preferably at least 95%. In addition, ethyl acetate may also be present in the first residue of line 118. The reboiler load decreases as the concentration of ethyl acetate in the first residue in line 118 increases. The first tower 115 also forms a pavilion that is drawn out of the pipeline up and can be, for example, 3〇:1 to 1:30 ratio 'from 1〇:1 to 1:1〇 or from 5:1 to 1:5 The ratio is condensed and refluxed. The higher mass to flow ratio of water to organic feed allows the first column 115 to operate at a reduced reflux ratio. The first distillate in line 119 is preferably acetaldehyde and ethyl acetate comprising a majority of the weight from liquid stream 113 and from ethyl acetate recycle stream 117. In one embodiment, the first distillate in line 119 comprises an ethyl acetate concentration that is less than the ethyl acetate concentration of the azeotrope of ethyl acetate and water, and more preferably less than 75% by weight. In some embodiments, the first distillate in line 119 also includes ethanol. Returning the first distillate comprising ethanol to the reactor may require an increase in reactor capacity to maintain the same level of ethanol efficiency. In a particular embodiment, ' preferably less than 1 〇 0/ from the crude ethanol stream. Ethanol, such as less than 5% or less than 1%, is returned to the reactor. When expressed in range. The amount of ethanol returned is the amount of ethanol in the crude ethanol stream. 〇1 to 1〇〇/. Such as 〇.1 to 5% or 〇2 to 1%. In one embodiment, to reduce the amount of ethanol returned, ethanol can be recovered from the first distillate in line U9. To recover the ethanol, as shown in Figure 1, the first distillate in line 119 is fed to the extractor 120 as needed. The extractor 12A includes an extraction column 121 to recover ethanol and reduce the concentration of ethanol recirculated to the reactor 130. The extraction column 12 can be a multi-stage extractor. In the extraction • 22· 201245127 column 121, the first distillate in line 119 is fed with at least one extractant 122. In a specific example, the extraction #U22 may be selected from the group consisting of benzene, propylene glycol, and a mixture thereof. Although water can be used, the extractant 122 preferably does not form an azeotrope with ethanol. Preferably, the extractant 122 is non-carcinogenic and non-toxic. Preferably, the extractant extracts ethanol from the first distillate in extract stream 124. The extractant can be recovered from the liquid stream 124 in the recovery column 123 and returned via line 125. The ethanol stream in line 126 can be combined with the ethanol product or returned to one of the distillation columns, such as first column 115. The raffinate 127 can be returned to the reaction zone ιοί. Preferably, the raffinate 127 comprising acetaldehyde and ethyl acetate is less ethanol than the first distillate in line 119. In one embodiment, the raffinate comprises less than 2% by weight of ethanol, such as less than 1% by weight of ethanol or less than 5% by weight of ethanol. Exemplary components of the composition and residue composition of the first column 115 are shown in Table 3 below. It should also be noted that the exhibits and residues of the museum may also contain other components not listed in Table 3. For convenience, the contents and residues of the first tower are also referred to as, the first distillate, or, the first residue. The other tower's full or residue may also be called similar Numbered modified substances (such as second, third, etc.) to distinguish between these 'but this modified substance should not be interpreted as requiring any specific separation order. -23- 201245127 Table 3: Light hydrocarbon tower concentration (% by weight) Concentration (% by weight Γ%, proud of ethyl acetate 10 to 85 15 to 80 20 to 75 acetaldehyde 0.1 to 70 0.2 to 65 0.5 to 65 acetal < 3 0.01 to 2 0.05 to 1.5 acetone < 0.05 0.001 To 〇.〇3 0.01 to 0.025 Ethanol <25 0-001 to 20 0.01 to 15 Water 0.1 to 20 1 to 15 2 to 1 〇 acetic acid < 2 < 0.1 < 0.05 Residue acetic acid 0·1 to 50 0.5 To 40 1 to 30 water 5 to 40 5 to 35 10 to 25 ethanol 10 to 75 15 to 70 20 to 65 0.08 to 1 ethyl acetate 0.005 to 30 〇. 〇 3 to the present invention - specific case towel 't- tower 115 can be removed in most of the water, ethanol and acetic acid · to the residue stream and only a small amount of ethanol and water are collected to the remainder The operation at the temperature is due to the formation of a two-phase and three-phase azeotrope. The weight ratio of water in the line 118 to the water in the distillate in line 119 can be greater than ι:1, such as greater than 2:1. When the optional extractant 116 is used, there is more water in the residue in line 118. The weight ratio of ethanol to ethanol in the distillate may be greater than 1:1, such as greater than 2:1. The amount of acetic acid in the residue may mainly vary depending on the conversion rate of the reactor 1〇3. In a specific example, when the total conversion rate is high, for example, higher than 90%, the amount of acetic acid in the first residue may be less than 10 % by weight, such as less than 5 weights ❶/〇 or less than 2. In one embodiment, when the conversion is lower, such as less than 90%, the amount of acetic acid in the first residue may be greater than 1% by weight. Preferably, the first distillate in 119 is substantially free of acetic acid, such as comprising less than 1000 ppm by weight, less than 500 ppm by weight, or less than 1 Torr by weight of acetic acid. The distillate can be purified from the system or all Or partially recycled to the reactor 103 ^ In some specific examples, when the distillate package • 24· 201245127 The simplification may be further separated into a stream of ethylene and a stream of acetic acid, such as a column (not shown), which may be returned to reaction (iv) 3 or separated from system 100 as an additional product. The flow can also be produced by hydrolysis or by hydrogen reduction via gasolysis. In the manufacture of additional ethanol, it is preferred to recover the additional ethanol without reactor 103. Some species, such as acetals, can be decomposed in the first column 115, leaving a very small amount of acetal or even no detectable amount in the distillate or residue. Further, an equilibrium reaction between ethanol and acetic acid can occur after the crude ethanol liquid stream is discharged from the reactor 103 or the first column 115. Without wishing to be bound by theory, ethyl acetate can be formed in the reboiler of the first column 115. Depending on the concentration of acetic acid in the crude ethanol stream, this equilibrium can be driven to the formation of ethyl acetate. This reaction can be adjusted via residence time and/or crude ethanol stream temperature. In a specific example, the balance facilitates esterification to produce ethyl acetate due to the composition of the first residue in line 118. Although the esterification can consume ethanol in the liquid or gas phase, the acetification can also reduce the amount of acetic acid that must be removed by the process. Ethyl acetate, which is autocatalyzed by the first column 115 and the second column 13, can be removed from the first column 115. The esterification reactor can be a liquid or vapor phase reactor and can include an acidic catalyst. An acid catalyzed esterification reaction can be used in some embodiments of the invention. The catalyst should be thermally stable at the reaction temperature. Suitable esterification catalysts can be solid acid catalysts, including ion exchange resins, zeolites, Lewis acids, metal oxides, inorganic salts and their hydrates, heteropolyacids and salts thereof. Silicone, aluminum oxide and aluminum phosphate are also suitable catalysts. Acid catalysts include, but are not limited to, sulfuric acid and p-toluene acid. In addition, Lewis acid can also be used as an esterification catalyst such as trifluoromethane (III) or trifluoromethyl (III), (IV) or (IV) salt, and an aryl group. Arene salt. The catalyst may also comprise an acid-reduced (continued acid) ion exchange resin (such as gel type and macroporous sulfonated styrene-divinylbenzene IERS), a sulfonated polyoxo-oxygen resin, and a sulfonated perfluorination (eg, Sulfonated poly-perfluoroethylene or sulfonated ruthenium oxide. The first residue in the line 118 for recovery can be further separated depending on the concentration of acetic acid and/or ethyl acetate. In most of the specific examples of the invention, the residue in line 118 is further separated in a second column 13 (also referred to as an "acid column"). The second column 130 produces a second residue comprising acetic acid and water in line 131 and a second -25-201245127 distillate comprising ethanol and ethyl acetate in line 132. In one embodiment, the majority of the weight of water and/or acetic acid fed to the second column 130 is removed to a second residue in line 131, such as at least 6% water and/or acetic acid is removed to The second residue in line 131, or more at least 8% water and/or acetic acid, is removed. The acid column may be desirable, e.g., when the acetic acid concentration in the first residue is greater than 5 〇 ppm by weight, such as greater than 0.1% by weight, greater than 丨 by weight, such as greater than 5% by weight. In a specific example, the first residue in line 118 can be preheated prior to introduction into second column 13, as shown in FIG. The preheating of the first residue in line 118 can be heated with the residue of second column 13〇 or the overhead vapor of first column 13〇. At least a portion of the first residue in line ns may pass through a secondary reactor 16 which is preferably a vapor phase esterification reactor or may be passed to a secondary vaporizer 161. The secondary reactor can include both a vaporizer and a vapor phase esterification reactor that produces a liquid stream in which at least a portion of the contents are a vapor phase. The secondary vaporizer 丨6丨 also produces a liquid stream in which at least a portion of the contents are vapor phases. The stream from the secondary reactor 丨6〇 and the secondary carburetor 161 can be combined with a portion of the first residue preheated in the bypass line 162. A portion of the vapor feed in line 163 preferably has less than 30 mole percent of the content as a vapor phase, such as less than 25 mole percent or less than 20 mole percent. When expressed in terms of ranges, from 1 to 3% of the moles are in the vapor phase, such as from 5 to 20 moles. /〇. The larger vapor phase content results in increased energy consumption and significantly increases the size of the second column 13〇. It should be understood that the preheating of Figure 2 can be combined with the features of the figures. Acetate formation in the first residue in line 118 increases the ethyl acetate concentration which results in an increase in the size of second column 130 and an increase in reboiler loading. Thus, acetic acid conversion can be controlled based on the initial ethyl acetate concentration withdrawn from the first column. In order to maintain effective separation, the ethyl acetate concentration of the first residue fed to line 118 of the second column is preferably less than 1 Torr (8) ppm by weight, such as less than 8 Torr ppm by weight or less than 6 Torr ppm by weight. The second column 130 is operated in such a manner that ethanol is concentrated from the first residue such that most of the ethanol is carried to the top of the column. Thus, the residue of second column 130 can have a low ethanol concentration of less than 5% by weight, such as less than 1% by weight or less than 0.5% by weight. Lower ethanol concentrations can be achieved without significantly increasing the reboiler duty or column size. Therefore, in some specific examples, the ethanol concentration in the residue can be effectively reduced to less than 5 〇 ppm by weight, or more preferably less than 25 ppm by weight. As described herein, the second column 1 residual _ can be reduced if and the reduced 6 melamine residue is treated without producing other impurities. -26- 201245127 The first residue in line 118 in Fig. 1 is introduced into the second column no, preferably at the top of the second column 130, at the top half or at the upper 丨/3. Feeding the first residue in line 118 into the lower portion of second column 130 does not necessarily increase the energy demand of the second column. Acid column 130 can be a plate column or a packed column. In Fig. 1, the second column 13' can be a plate-like column having a theoretical plate number of 1 〇 to 11 ,, such as from 15 to 95 theoretical plates or from 20 to 75 theoretical plates. An additional plate can be used if it is desired to further reduce the ethanol concentration in the residue. In a specific example, the retarder load and column size can be reduced by reducing the number of plates. Although the temperature and pressure of the second column 130 may vary, the temperature of the second residue in the line 丄" at atmospheric pressure is preferably from 95 ° C to 160 ° C, such as from 100 ° C to 150 ° C. Or from 110C to 145 ° C. In a specific example, when the first residue in line 118 is preheated to a temperature within 2 ° C of the temperature of the second residue of line 131, such as within i5 ° c Or the temperature of the second distillate flowing out of the line 132 of the second column 130 is preferably from 50 ° C to 12 (TC, such as 75 ° C to 118 ° C or from 8 CTC to 115. (: The temperature gradient at the base of the second tower 130 may be steep. The pressure of the second tower 130 may range from 11 kilobar (kpa) to 51 〇 kPa (for example, 1 kilobar (kPa) to 475 kilobars (kPa) or ranging from 1 kilobar (kpa) to 375 kilobars (kpa). In one embodiment, the second tower 130 is operated at above atmospheric pressure, such as high At 17 〇 (bar 3) or

The bureau is at 375 kilobars (kPa). The second column 130 can be constructed of materials such as 316L SS, Allot 2205 or Hastelloy C, depending on the operating pressure. The reboiler duty and column size for the second column 130 can be maintained relatively constant until the ethanol concentration in the second distillate in line 132 is greater than 9 Torr weight 0/Torr. In a specific case, the first column 115 is preferably an extraction column using water. The additional water system is separated in the second column 130. Although the use of water as an extractant can reduce the reboiler loading of the first column 115, when the mass to flow ratio of water to organic feed is greater than 〇65:1, such as greater than 0.6:1 or greater than 0.54:1, additional water will This causes an increase in the reboiler duty of the second column 13 which will offset any benefit obtained by the first column 115. The second column 130 also forms an overhead which is drawn out of line 133 and which may, for example, be 12:1 to 1:12' condensed and refluxed from 10:1 to 1:10 or from 8:1 to 1:8. . Preferably, the overhead in line 133 comprises from 85 to 92% by weight ethanol, such as from about 87 to about 9 weight percent ethanol, with the balance being water and ethyl acetate. -27· 201245127 In one embodiment, water can be removed prior to recovery of the ethanol product. In one embodiment, the overhead in line 133 may comprise less than 15% by weight water, such as less than 1% by weight water or less than 8% by weight water. As shown in Figure 1, the overhead vapor in line 133 can be fed to a water separator 135, which can be an absorption unit, membrane, molecular sieve, extractive distillation column, or a combination thereof. In one embodiment, at least 50% of the overhead steam is fed into the water separator 135, such as at least 75% or at least 90%. Optionally, some of the overhead vapor in line 133 is condensed to a second distillate 132 and may be fed directly to third distillation column 14 视 as appropriate. The water separator 135 in Fig. 1 may be a pressure swing adsorption (PSA) unit. The details of the PSA unit are not shown in the drawings for purposes of illustration. The psa unit is optionally from 3 〇 ° c to 160. (3, such as from 80 C to 140 ° C and from 0.01 kPa (kPa) to 550 kPa (kPa), such as from 1 kilobar (kPa) to 150 kilobar (kPa) pressure. pSA The unit may include two to five beds. The water separator 135 may remove at least 95% of the water from the overhead vapor 133 and preferably remove from 95% to 99.99% of the water from the overhead vapor 133, and remove to The aqueous stream 134, all or part of the aqueous stream 134, may be returned to the second column 130 in line 136, which may increase the reboiler duty and/or the size of the second column 130. Additionally or alternatively, all or part of the liquid The stream may be purged via line 137. The remaining portion of the vapor column overhead 133 exits the water separator 135 in an ethanol mixture stream 138. In one embodiment, the ethanol mixture stream 138 includes more than 92% by weight ethanol, such as more 95% by weight or more than 99% by weight. In one embodiment, a portion of the aqueous stream 137 can be fed to the first column 115 as an extractant (not shown). The portion of the vapor column overhead 133 can be, for example, from about 12:1. To 1:12, such as from ι〇:ι to ι:1〇 or from 8:1 to 1:8, condense and reflux to the second tower of the household. The middle of the pipeline 132 The exhibits may optionally be mixed with the ethanol mixture stream 13 8 and co-fed to the product column 140. This may be necessary if additional water is required to improve the separation in the product column 14 。. It should be understood that the reflux ratio may vary with the number of stages, Feed position, column efficiency, and/or feed composition may vary. Operation at reflux ratios greater than 3:1 may be less desirable as more energy may be required to operate second column 130. Example of ethanol mixture stream 138 The composition of the components and the residue of the second column 130 are shown in Table 4 below. It should be understood that the distillate and the residue may also contain other components not listed in Table 4. For example, in the specific case, when acetic acid B When the ester is fed to the reactor 1〇3, the second residue in the line 131 as exemplified in Table 4 may also include the high boiling component concentration (% by weight). I Alcohol mixture flow table 4: acid Tower concentration _ (% by weight) concentration (weight ethanol ethyl acetate acetaldehyde water acetal second residue acetic acid water ethyl acetate ethanol 90 to 99.9 &lt; 10 &lt; 10 &lt; 10 &lt; 2 92 to 99 0.001 to 5 0.001 to 5 0.001 to 3 0.001 to 1 96 to 99 0.005 to 4 0.005 4 〇·〇1 to 1 0.005 to 0.5 0.1 to 45 45 to 1〇〇&lt;0.1 &lt;5 0.2 to 40 55 to 99.8 0.0001 to 0.05 0.002 to 1 0.5 to 35 65 to 99.5 0.0001 to 0.01 ^ to 0.5 ethanol mixture The weight ratio of ethanol in stream 138 to ethanol in the second residue in line 131 is preferably at least 35:1. Preferably, the ethanol mixture stream 138 is substantially free of acetic acid and may contain traces of acetic acid, if any. In a specific example, the ethyl acetate fed to the second column 13 can be concentrated in the top of the steam column and passed through the mixture with the ethanol. Thus, the difficulty is (10) the second age is extracted to the second of the line 131. Residue. This will advantageously allow most of the ethyl acetate to be subsequently recovered without further processing of the second residue in line 131. The feed to reactor 103 may include acetic acid and/or ethyl acetate, as appropriate. When ethyl acetate is used as the feed alone, the crude ethanol product may substantially exclude water and/or acetic acid. There may be high boiling components such as alcohols having more than 2 carbon atoms such as n-propyl, isopropanol, n-T alcohol, 2-T alcohol and mixtures thereof. The high-lying component means a compound having a boiling point in ethanol. This high boiling component can be removed in the second column 13(R) to a second residue in line 131 of 29-201245127 as described herein. As described above, according to the present invention, the unreacted acid (also referred to as dilute acid stream) in the second residue in the line 131 is introduced into the esterification unit 120. In some embodiments, the second residue in line 131 can include at least 85% acetic acid from crude ethanol stream 109, such as at least 9% and preferably at least 99%. When viewed in terms, the dilute acid stream includes from 85% to 99.5% or from 90% to 99.99% of unreacted acetic acid from the crude ethanol stream. In one embodiment, substantially all of the unreacted acetic acid is recovered in the second residue in line 131. By removing substantially all of the unreacted acetic acid from the crude ethanol stream 109, the process advantageously does not require further separation of the acetic acid from the ethanol. In some embodiments, the dilute acid stream comprises from 1 to 55 weight percent acetic acid and from 45 to 99 weight percent. / 〇 water. In one embodiment, substantially all of the unreacted acetic acid is reacted in the second residue of line 13丨. According to Fig. 1, a second residue in line 131 is fed together with alcohol stream 151 to esterification unit 150' to produce an ester product stream 152 comprising one or more esters and a bottoms substrate 153 comprising water. By way of specific example, ester product stream 152 and/or bottoms 153 may be substantially free of acetic acid. The second residue in line 131 can be fed to the esterification unit 150 at a temperature of from 2 Torr to 90 °C. Preheating can be used if desired. In some embodiments, the alcohol residue 151 and the second residue in line 131 are fed to the esterification unit in a countercurrent manner to promote the production of the reaction product. In another embodiment, it is not shown that the alcohol stream 151 can be added directly to the first residue of line 131 prior to introduction into the esterification unit. The alcohol in the alcohol stream 151 can be any suitable alcohol such as methanol, ethanol, propanol, butanol or mixtures thereof. Preferably, the alcohol is a sterol. In some embodiments, the esterification unit 150 includes a reaction zone that includes a reactor coupled to a separation zone comprising one or more of a retort and/or a stripper. Suitable reactors for this esterification include batch reactors, continuous feed to stirred tank reactors, column flow reactors, reactive distillation columns, or combinations thereof. In some embodiments, an acid catalyst is fed to the reactor to accelerate the esterification of the acetic acid. Suitable acid catalysts for use in the present invention include, but are not limited to, sulfuric acid, phosphoric acid, sulfonic acids, heteropolyacids, other inorganic acids, and combinations thereof. The residence time of the esterification unit 150 can affect the acetic acid conversion. In some specific examples, for example, the residence time in the S-factor unit 150 is from 〇] to 5 hours, such as from 2 to 3 hours, or less than 丄 hours. The distillation column of the esterification unit 150 of 201245127 may include 5 to 70 theoretical plates, such as from (7) to the theoretical number of plates or from 15 to 30 theoretical plates. The reflux of ester product stream 152 can be from (7): 丨 to 丨·丨〇, such as from 5:1 to 1:5, or from 2:1 to 1:2. The operating parameters of the 'esterification unit 150' can be varied to achieve the desired composition in the ester product stream i52. For example, 'some specific shots. Temperature, diligence, feed rate and residence time can be varied to increase the conversion of acetic acid to ester, reduce impurity formation, achieve more efficient separation, reduce energy consumption, or a combination thereof. In a specific example, the esterification unit 150 is operated at a substrate temperature of from 1〇〇1 to 15〇(&gt;: as from 100 ° C to 130 ° C ' or from 10 (TC to 120 ° C. The pressure indicates that the acetalization unit 15 can be operated at atmospheric pressure, subatmospheric pressure or super-atmospheric pressure. For example, in some specific examples, the esterification unit 150 is in a sentence from 50 kPa to 500 kPa, such as Operating at pressures from 5 〇 to 400 kPa (kPa) or from 50 kPa (kpa) to 2 〇〇 kPa. In some specific examples, the feed rate of acetic acid and alcohol to the acetal unit It can be adjusted to control the molar ratio of acetic acid to alcohol fed to the acetating unit 150. For example, in some embodiments, the molar ratio of acetic acid to methanol fed to the acetating unit 150 is from 1:1 to 1:5. 〇, such as from ^ to (9) from 1:5 to 1:20. ^ ^ The process of the present invention preferably provides a high conversion of acetic acid to vinegar... In the specific example, the third residue of the line 131 is at least secret, For example, at least 7 (%), at least 9%, or at least 95% of the acetic acid is converted to vinegar. If line 132 is known to have a relatively low concentration of acetic acid in the second residue, the low conversion of acetic acid can be tolerated. The 150 vinegar product 152 is preferred to include at least the purpose of the smear. When using methanol as the spur flow 151 of the S unit, the exemplified test results are shown in Table 5 below. It should be understood that the composition may also be Contains other components not listed in Table 5. When a higher concentration of alcohol is fed to the reactor relative to the acetic acid to be reacted, a smaller amount is possible. When the excess alcohol is associated with the second residue from line 131 When acetic acid is reacted, some alcohol may be present in the vinegar product stream 152. • 31- 201245127 Ester product liquid 浠 Table 5: Esterification unit 15 〇 Concentration concentration Acetyl acetate 1 1 to 90 5 to 85 sterol 40 to 99.9 45 to 95 water &lt;1 0.001 to 0.5 acetic acid &lt; 0.1 &lt; 0.5 m &lt; 1 0.001 to 0.5 column substrate water 90 to 99.9 92 to 99.9 acetic acid &lt; 5 0.001 to 3 sterol &lt;1 &lt; 0.001 &lt;;0.05 acetic acid &&lt;1 95 to 99.9 0.01 to i not measured -^22〇i_^〇〇〇5 concentration!**%)_ to 9〇5〇 to 9〇0.001 to 〇1 0.001 to 〇1 is detected. In the vinegar unit 15G reaction, some impurities such as two may be formed. The quality may exist in a very small amount or even It may be present in a fine amount in the product stream 152. In this particular embodiment, the vine product stream 152 comprises less than the surface weight ppm of dimethyl (tetra), such as less than ^ ppm by weight or less than 500 ppm by weight. In some specific examples, the S-factor unit 15 includes a reaction steam tower. The reaction steam scale includes an ion exchange bed, a heterogeneous combination. A non-limiting example of a fresh resin based on this side of the test includes a macroporous strong acid cation exchange resin from Rohm and Haas Company's Amberfyst®. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; In other embodiments, the reactive steaming tower comprises a group selected from the group consisting of sulfuric acid, glacial acid, can acid, heteropolyacids, other inorganic acids, and combinations thereof. In another specific embodiment, the acidic catalyst comprises a zeolite and a support treated with a mineral acid and a heteropolymer. When an acid catalyst such as sulfuric acid is used, the acid phase medium is fed into the reactive distillation column. In some embodiments, the second residue in line 131 is fed to a guard bed (not shown) as appropriate and then fed to esterification unit 150. In this respect, the guard bed comprises an ion exchange tree • 32- 201245127 grease as described above. Although not wishing to be bound by any particular theory, the guard bed removes one or more of the rosin metal present in the second residue in line 131, thereby allowing any ion exchange of the ion exchange resin towels present in the esterification unit 150. Deactivation of the catalytic site of the resin is minimized. Tower substrate 153 includes water and may be substantially free of acetic acid. In a specific example, a portion of the bottoms 153 of the line 154 may be directed to the first column 115 as an optional extraction core. The bottom substrate 153 may be used for hydrolysis including acetic acid or a second The flow of the secret. The column substrate 153 can pass through the towels and the domains before being discarded for disposal in the wastewater treatment. The organic content of the bottoms (5), such as the acetic acid content, can be used by microorganisms used in wastewater treatment plants. As noted above, the ester product stream 152 can be further processed and/or refined. In one embodiment, the vinegar product stream 152 is fed to the chemical conversion process together with the carbon oxide to produce acetic acid. This allows the unreacted ethic to be indirectly transferred from the hybridization process to the hydrogenation process and the nitridation process. According to the specific case of the case, from the purpose product 152, Qianxian County can form ethanol by moth. The resulting ethanol can be removed or recycled to the process towel, such as to the first column 115, the second column 130, or the esterification unit 150. In one embodiment, an additional third column 140 can be used due to the presence of ethyl acetate in the ethanol mixture stream 138. The third column 140 is referred to as a "lightends" column and is used to remove ethyl acetate from the ethanol mixture stream 138 and produce an ethanol product in a third residue of line 141. The product column 140 can be a plate tower or a packed tower. In the figure, the third column 14〇 can be a plate tower having a theoretical plate number of 5 to 90, such as a theoretical plate number from 1〇 to 6〇 or a theoretical plate number from 15 to 5〇. The feed position of the ethanol mixture stream 138 may vary depending on the ethyl acetate concentration and preferably the ethanol mixture stream 138 is fed to the upper portion of the third column 140. Higher concentrations of ethyl acetate may be fed to the second column. The two positions of 140. The feeding position should avoid the extreme upper plate and close to the recirculation, avoiding the excessive load demand on the tower and increasing the tower size. For example, in a tower with 45 exact plates, the feeding position should be Between the 10th and 15th plates from the top. Feeds above this point may increase reboiler loading and light hydrocarbon column 140 size. Ethanol mixture stream 138 can be up to 70t, such as up to 50°C Or at a temperature of up to 40 ° C -33- 201245127 1 into the pre-Tower fortune. There is a turn _ towel, material «in-step ^_ compound The liquid stream acetic acid can be concentrated in the pipeline 142 r; r; r * r · --- ί-^ ΐ ί: ί 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶 蝴蝶The three-touch can be purified as an additional product in the tube _, such as acetic acid, from the system. To the recovered ethanol material, the third substance in the 142 is returned to n and can be similar to that shown in Figure 丨. The extraction column is used to recover ethanol. Some of the other specifics in the middle line 142 can be purified from the system as a solvent such as ethyl acetate in line 143. In addition, an extractant such as benzene can be prepared. Propylene glycol and ^ ΪϋΪ ΪϋΪ ΪϋΪ 。 。 。 。 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 142 It is desirable to have the third unit, the membrane, or a combination thereof, which is further from the line 141. Most of the specific shots are used to remove water prior to the third column (10) using the water recording 135 and thus do not require further drying of the ethanol. The three towers 14 are preferably plate-shaped towers as described above and preferably operated at atmospheric pressure. The temperature of the third residue in the line (4) from which the column 140 flows out is preferably from pit to 1 thief, such as from 70. (: to 1 〇〇. (: or from 751 to 8 〇. (:: from the third The temperature of the third arrogant in the pipeline 142 flowing out of the tower 14 is preferably from the thief to the thief, such as from 50t to 65. The pressure of the second tower 140 can be from oj 千 ((4) to 51 The range of kpa, such as from kilocalories (kPa) to 475 kilobars (kPa) or from 1 kilobar (kPa) to 375 kilobars (kpa). In some embodiments, the second tower 140 may Operating at a vacuum below 7 〇 kPa (kpa), such as below 5 〇 kPa ((iv)) or below, such as kilo kPa (kPa). Lowering the operating temperature substantially reduces the column diameter and the reboiler duty of the third column - 34 - 201245127. The example components of the ethanol mixture stream and the residue components of the third column 140 are shown in the table below. 6 ° It is understood that the distillate and the residue also contain other components not listed in Table 6. ~~ Table 6: Product Tower ~~ Concentration (% by weight) Concentration (% by weight) Concentration (% by weight) Distillate Ethanol 70 to 90 72 to 90 75 to 85 Ethyl acetate 0.5 to 30 1 to 25 1 to 15 B Aldehyde &lt;15 0.001 to 10 0.1 to 5 water &lt;10 0.001 to 2 0.01 to 1 acetal &lt; 2 0.001 to 1 〇.〇1 to 0.5

Ethanol 80 to 99.5 85 to 97 90 to 95 water &lt;8 0.001 to 3 〇_〇1 to 1 ethyl acetate &lt;1.5 0.0001 to 1 0.001 to 0.5 acetic acid &lt;0.5 &lt;0.01 0.0001 to 〇.〇1 When the pipeline The first residue in 118 comprises a low level of acetic acid and/or the first residue is substantially free of acetalization such that the ethyl acetate concentration is less than 5 〇 ppm by weight, and the third column 14 is optional. Thus, the ethanol mixture stream 138 obtained from the water separator 135 can be an ethanol product and is free of an acetic acid recycle stream. Depending on the amount of water and acetic acid contained in the second residue in line 131, it may be treated in one or more of the following processes. One of the processes including the esterification unit 15 is shown in the figure. Suitable weak acid recovery streams are described in U.S. Publication No. 2012/0010446, the disclosure of which is incorporated herein by reference. When the residue comprises a majority of acetic acid, such as more than 70% by weight, the residue can be recycled to the reactor without any water separation. In one embodiment, when the residue comprises a majority of acetic acid, such as more than 5% by weight, the residue can be separated into an acetic acid stream and a water-35-201245127 stream. In some embodiments, acetic acid may also be recovered from the first residue having a lower acetic acid concentration. The residue can be separated into (iv) and aqueous streams by steaming or - or multiple membranes. If a membrane or membrane array is used to separate the acetic acid from the water, the face or membrane array can be selected from any suitable acid resistant membrane that can remove the permeate stream. The resulting acetic acid liquid stream was returned to the reactor 1〇3 as the case may be. The resulting aqueous liquid can be used as an extractant or to hydrolyze an ester-containing liquid stream in a hydrolysis unit. In other specific examples, such as when the second residue in line 131 comprises less than 5 Torr of weight per gram of acetic acid, the 'possible options include the following - or more: (丨) returning a portion of the residue to reactor 103 (()) neutralize B., (10) react acetic acid with an alcohol, or discard the residue in a wastewater treatment plant. It is also possible to separate the residue comprising less than 5% by weight of acetic acid by means of a weak acid recovery steaming tower which can be added with a solvent (as a boiling azeotrope). Exemplary containers suitable for this purpose include ethyl acetate, acetonitrile, isopropyl acetate, butyl acetate, vinyl acetate, dipropyl ether, carbon disulfide, tetrahydrofuran, isopropanol, ethanol, and c3-c12 alkanes. . Preferably, when neutralizing acetic acid, the residue in line 131 comprises less than 10 weights of 0/0 acetic acid. The acetic acid can be neutralized with any suitable alkali or alkaline earth metal base such as sodium hydroxide or potassium hydroxide. When the acetate scale is reacted, it is preferred that the residue comprises less than 5 G weight percent acetic acid. Alcohol I is any suitable alcohol such as methanol, ethanol, propanol, butanol or mixtures thereof. The reaction forms a stipulation that it can be integrated with its gift, such as an age-old manufacturing or ester manufacturing process. Preferably, the alcohol comprises ethanol and the resulting @ is intended to include (4) B. Depending on the situation, the contact can be fed to the hydrogenation reactor. In some embodiments, when the residue in line 131 comprises a very small amount of acetic acid, such as less than 5% by weight or less than 1% by weight, the residue may be neutralized and/or diluted prior to disposal in a wastewater treatment plant. The organic content of the residue, such as the acetic acid content, may be advantageously suitable for cultivating microorganisms in a wastewater treatment plant. The associated condenser and liquid separation vessel that can be used with each distillation column can be of any conventional design and simplifies the closure. Heat can be applied to each column substrate or to the bottom of the loop via a heat exchanger or reboiler. Can be other than the other side (four) such as the internal county ^. The heat supplied to the resolver can be derived from any heat generated by the process of reboiling H__body or from external sources such as other heat or reheating that generates heat. Although a reactor and a flasher are shown in the system, additional reactors, flashers, condensers, heating elements, and other components can be used in various embodiments of the invention. As is well understood by the art, the -36-201245127 inlet, machine, reboiler, drum, valve, connector, separation vessel, etc. can also be combined and made in the process of the invention. The temperature and pressure used in the tower can be transferred. The range between each zone = the composition and the boiling point of the composition removed by the residue. For example, the temperature at the predetermined position of the steaming tower is shouted with the pressure of the material at that position. Material, the speed lining is determined by the ruler and is generally referred to as the feed weight ratio. The ethanol product described in the Xi'an process can be industrial grade ethanol or fuel grade ethanol. The range of 7G to ethanol compositions is shown in Table 7 below. Soap η^---- Clothes 7. Completed ethanol composition" Agricultural concentration component Ethanol acetic acid ethyl acetate acetal acetone isopropanol n-propanol 85 to 99.9 &lt;8 &lt;1 &lt;2 &lt;2 &lt;0.05 &lt;0.05 &lt;0.5 &lt;0.5 &lt;0.5 90 to 99.5 0.1 to 3 &lt; 0.1 &lt; 0.5 &lt; 0.01 &lt; 0.01 &lt; 0.1 &lt; 0.1 Concentration (% by weight) 92 to 99.5 0.1 to 1 &lt; 0.01 &lt; 0.05 &lt; 0.005 &lt;0.005 &lt;0.05 &lt;0.05 The composition of the ethanol of February and February is preferably a very small amount such as less than 5%. 5% by weight of you |:, ^ 曱 佑 I I, I Butanol, isoamyl alcohol and other C4-C2° alcohols. The specific amount in the specific % to B' composition is from 8G to (10) ppm by weight, such as from _m SPPm, from 100 to 700 ppm by weight, or from 150 to 500 ppm by weight. In the system, the finished biaxial product is substantially free of ", as the case may include less than 8 weights, such as less than 5 ppm by weight or less than 1 ppm by weight. The finished ethanol composition prepared by the specific example of the month can be used for various purposes, including "', ',,, '·, paving, chemical raw materials, (4) products, detergents, aging agents, hydrogen transfer or •37·201245127 For consumption, etc. In fuel applications, the finished ethanol composition can be blended with gasoline for vehicles such as automobiles, boats and small piston engine aircraft. For non-fuel applications, this finished ethanol composition can be used as a hygiene and makeup Formulations, detergents, disinfectants, coatings, inks, and pharmaceutical solvents. The finished ethanol composition can also be used as a processing solvent in the manufacturing process of pharmaceutical products, food preparations, dyes, photochemicals, and latex processing. The ethanol composition can also be used as a chemical raw material to manufacture other chemicals such as vinegar, ethyl enoate, ethyl acetate, glycol ethers, ethylamines, aldehydes, and higher alcohols, especially butanol. In ethyl acetate, the completed ethanol composition can be esterified with acetic acid. In other applications, the finished ethanol composition can be dehydrated to produce ethylene. The invention will be apparent to those skilled in the art and in the scope of the present invention. Each of the pavings may be combined or exchanged in whole or in part. The specific examples of the other specific examples may be appropriately combined with the other specific examples, which are well known to those skilled in the art. In addition, those skilled in the art will understand that the foregoing description is only illustrative and is not intended to limit the invention. The invention will be more fully understood by reference to the following. In the drawings, the same reference numerals indicate similar components. Fig. 1 is a schematic view showing an ethanol production system having a plurality of steaming towers including an acid tower and a water separator for recovering ethanol according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION - An example of an ethanol manufacturing system having a plurality of column tests having a process for vaporizing at least a portion of the feed to a second column. 38-201245127 [Main component symbols Description] Code Description 100 Hydrogenation System 101 Reaction Zone 102 Separation Zone 103 Reactor 104 Vaporizer 105 Line 106 Line 107 Line 108 Line Discharge Line 109 Line / Ethanol Stream 110 Separator 112 Steam Stream 113 Liquid Stream 115 First Distillation Tower / First Column 116 Extractant 117 Ethyl acetate recycle stream 118 Residue stream 119 Line 120 Extractor 121 Extraction column 122 Extractant 123 Recovery column • 39· 201245127 Code description 125 Line 126 Line 127 Raffinate 130 Second distillation column / Second column 132 second distillate 133 line/steam bottoms 134 water stream 135 water separator 136 line 137 line 138 ethanol mixture stream 140 product column 141 line 142 line 150 esterification unit 151 alcohol stream 152 ester Product stream 153 column substrate 154 pipeline

Claims (1)

201245127 VII. Patent application scope: 1. A process for producing ethanol, comprising: hydrogenating acetic acid and/or its ester in a reactor in the presence of a catalyst to form a crude ethanol liquid stream; separating in a first steaming tower a portion of the crude ethanol stream to obtain a first-column comprising acetaldehyde, ethyl acetate and ethanol, and a first residue comprising ethanol, acetic acid and ethyl acetate; Obtaining a second residue comprising acetic acid and a second distillate comprising ethanol and ethyl acetate; and separating at least a portion of the second extract in the third steaming to obtain a second residue of ethyl acetate and a third residue comprising ethanol; wherein the first product is returned to the reverse yarn and less than 10% of the ethanol from the crude ethylene stream is returned to the reactor. 2. 3. 4. 5. 6. Less than 5% As in the process of claim 1, the ethanol from the crude ethanol stream is returned to the reactor.嶋之自至=的请乙专; 1 关第丨^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ====: Into, the first - _ as the patent application scope of the seventh process, ethanol. Wherein the raffinate stream comprises less than 2% by weight of 9. H-valve such as fine 'its shirt' (10) residual liquid flow returns to 201245127 ΐα:=: Process of item 7 'where at least part of the ethanol stream is The process of the item 'will be at least part of - 12. to _ there is acetic acid 14. | 2_ is the process of item 13. The first steamed plum tower, the second steamer tower 3 second The total diameter of the steamed hunger is 5 to hm, and further the ratio of the total tower diameter of the first steaming tower, the 14.2 tower and the third tower to the number of ethanol nozzles produced per hour is from 1 : 2 to i: 3〇. A process for producing ethanol, which comprises: argonizing acetic acid in the reverse yarn in the presence of a medium, and forming a crude ethanol liquid =:: the crude portion of the separated portion of the column Ethanol (4) to obtain a first residue comprising acetyl chloride and ethyl acetate and including ethanol, acetic acid and water; the first residue is converted into a portion of the vapor phase having less than the ear % of the vapor Dissolving the portion of the vapor feed in the fj solution to obtain a first residue comprising acetic acid and a second distillate comprising ethanol; The ethanol is recovered from the ethanol distillate. The process of claim 14, wherein a portion of the first residue is fed to the secondary reactor to convert at least some of the contents to a vapor phase. ·=Please apply the process of the patent Gu Di丨 5, which is the steam phase acetification reactor. 17.2 Please refer to the process of the 14th patent range, in which part of the first residue is fed into the secondary The /νί匕 device converts at least some of the contents into a vapor phase. 18. ^ The process of claim 4, wherein the portion of the steam feed has less than 25 moles in the vapor phase. Contents 19. In the process of applying for the scope of patent No. 14, the part of the steam is fed into the vapor phase and has a content of from 0.1 to 30 mol%. 20. 21. 22. ^ The process of claim 14, further comprising: using the adsorption unit, the membrane, the extracted steam scale, the molecular sieve or a combination thereof, removing water from at least a portion of the second library to produce a ratio of at least a portion Second, the liquid flow of the water with less water content The process of item 14 of the ttlt patent range, further comprising separating the second distillate from the third distillation column to obtain a third distillate comprising ethyl acetate and a third residue comprising ethanol. If the patent application is in the 14th item, the towel returns the first reading to the reverse wire, and returns to the reactor in the secret ethanol system, wherein the flow from the crude ethanol liquid is less.