TW201245128A - Reduced energy alcohol separation process having water removal - Google Patents

Abstract

The present invention relates to the recovery of alcohols, in particular ethanol, from a crude ethanol product obtained from the hydrogenation of acetic acid using a reduced energy process. The crude ethanol product may be fed to a distillation column in which a substantial portion of the water is removed with the acetic acid in the residue. Additional water may be removed by using a pressure swing adsorption unit, molecular sieve, and/or membrane. Ethanol extraction may also be used to reduce the ethanol concentration in the recycle streams.

Description

201245128 (b) Brief description of the symbol of the representative figure: Code description 100 Nitriding system 101 Reaction zone 102 Separation zone 103 Reactor 104 Hydrogen feed line / line 105 Acetic acid feed line / line 106 Separator 107 First tower 108 Vaporizer 109 Line 110 Line 111 Steam stream 112 Liquid stream 113 Line 114 Line 115 Light hydrocarbon tower / Second tower 116 Line 117 Line 121 Water separation unit 122 Water stream 123 Ethanol product stream 5. If there is a chemical formula in this case, please reveal Chemical formula that best shows the characteristics of the invention: Benefits 0 VI. Description of the invention: 201245128 Priority claims [Technical field to which the invention pertains] and in particular relating to water shifting The present invention generally relates to a process for the manufacture of alcohols, in addition to the step of recovering ethanol Low energy process. [Prior Art] Industrial ethanol is prepared from organic sources such as petroleum, natural gas, or occupational sources, or from sources such as syngas or self-property silty materials or cellulosic materials such as corn or sorghum. . Conventional methods for producing ethanol from organic sources and from cellulosic materials include ethylene oxide catalyzed hydration, methanol homologation, direct alcohol synthesis, and Fischer-Tropsch synthesis. The unstable price of petrochemical sources has caused the price of ethanol produced by the law to fluctuate, which makes the alternative energy source for ethanol production more demanding when the source price increases. The starchy material and the cellulose material are converted into ethanol by fermentation. However, fermentation is generally used in the manufacture of > xiaofei ethanol. The resulting yoke is suitable for fuel or human consumption. In addition, the fermentation of the starchy foods competes with the source of the food and limits the amount of ethanol that can be produced 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 such as 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 a hydrogenation process, esters are 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 unreacted acid will remain in the crude ethanol product' and it 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 201245128 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 ethyl acetate which will be recycled to the hydrogenation reactor. No. 7,842,844 describes a process for the conversion of hydrocarbons to ethanol and, where appropriate, to acetic acid in the presence of a particulate catalyst, which improves the selectivity and catalytic activity and operating life through syngas. An intermediate step is made. There is still a need for an improved process for recovering ethanol by reducing the crude product obtained from the reduction of alkanoic acids such as acetic acid and/or other carbonyl containing compounds. SUMMARY OF THE INVENTION In a first embodiment, the present invention relates to a process for producing ethanol, comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form ethanol, ethyl acetate, acetic acid, and water. Crude ethanol product; separating at least a portion of the crude ethanol product into a first distillate comprising ethanol, ethyl acetate, and at least 5% by weight water, and a first residue comprising acetic acid and water The majority of the water in the crude ethanol product of the lover is removed from the first precursor; at least a portion of the sputum is separated into a second residue comprising ethanol and water in the second retort, and includes a second column of acetic acid; and a water removal unit selected from the group consisting of an adsorption unit, a membrane, a molecular sieve, and combinations thereof. The second residue removal phase forms an ethanol product stream. , but the condition is that if the water is not removed from the first postal product before the second steaming, the specific water in the crude ethanol product is moved to the water in the first residue stream = Better than at least 5% water In addition. A second ram of the vapor portion can be fed into the water removal unit. In a specific example, the invention relates to a process for producing ethanol, comprising the following steps: broad [alcohol, acetic acid ethyl acetate, acetic acid and water crude ethanol product; separating at least the crude ethanol product into ethanol, The acetic acid ethyl acetate and the at least 5 water alcohol first alcohol product f, and the water system including the acetic acid and the water U residue 'the majority of the crude B of the tower are removed from the first residue (four); The first product is separated into a second residue comprising ethanol and water in the second steaming tower, and a second extract comprising the meaning of B-4-201245128; and a water removal unit is used a group of free adsorption units, membranes, sub-screens, and combinations thereof, from which the second residue removes water to form an ethanol stream', but the condition is such that it is not before the second steaming, In a third specific example of the present invention, the present invention relates to a process for producing ethanol, comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form ethanol, acetic acid, acetic acid, and Hydrogen produced ethanol; at least part of the coarse in the tower Ethanol production = separation into the first __ sheds including ethanol, acetic acid, and at least 5% by weight of water, and the first and fourth residues including acetic acid and water, and the towel is fed to the tower. Part of the water is removed from the first residue; at least a portion of the first fines are formed into a second residue comprising ethanol and water, and a second axis water removal unit comprising acetic acid A group of free absorbent elements, membranes, molecules, and combinations thereof, from which the second residue removes water to form an ethanol product stream. In a fourth embodiment, the invention relates to a process for producing ethanol, comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form a crude ethanol comprising ethanol, ethyl acetate SJ, acetic acid and water; a product; at least a portion of the crude ethanol produced in the column = separated into ethanol, acetic acid, and 5% by weight of water, and the first residue including acetic acid and water. The majority of the water of the crude ethanol product towel of the column is removed from the first residue; at least a portion of the first precipitate is separated into a second residue comprising ethanol and water in the second steaming, and includes a second distillate of ethyl acetate and ethanol; and extracting ethanol from the second steaming tower to provide an ethanol-free affinate). = In the specific example, 'the raffinate 9 is returned to the reactor' and the raffinate may have an ethanol concentration lower than the ethanol concentration of the first distillate, for example, an ethanol concentration of less than 2 wt%. [Embodiment] Introduction The present invention relates to a process for recovering ethanol obtained by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction obtains a crude product including ethanol, water, acetic acid, unreacted acetic acid and other impurities. Ethanol product. To improve operational efficiency, the process of the present invention involves separating the crude ethanol product into a residue stream comprising water and acetic acid and a distillate stream comprising ethanol. 201245128 Separate other organic impurities from the distillate stream in a subsequent column and collect ethanol with water at the bottom of the column. In a specific embodiment of the invention, the water adsorption unit is selected from the group consisting of adsorption units, membranes, molecular sieves, and combinations thereof to remove water. Preferably, the feed to the water removal unit is from a portion of the vapor reflux of the upper end of the light hydrocarbon column. Advantageously, this method of partitioning can result in a reduction in the energy demand for recovering ethanol from the crude ethanol product. For the purposes of the present invention, it is advantageous to remove water from the alcohol produced once the acetic acid and organic impurities are removed. Although some water can be removed together with acetic acid and organic impurities, it is preferred to remove water from B in the final step. The moisture feed may be at least 75% water', e.g., at least 80% or at least 9%, from the vapor reflux of the reactor. From the drying of the water separation unit, the water ethanol can be suitably used as red #ethanol or as a pilot oil blended with aviation fuel. The dry dehydrated ethanol may comprise less than 8 s% water, such as less than _%, less than 3 lbs of water. In the recovery of ethanol, the process of the present invention uses one or more distillation columns. Since the initial (first) tower. The crude ethanol product in the residue stream removes unreacted acetic acid and reduces the reaction that would consume the dried dehydrated ethanol product. In a preferred embodiment, the residue stream comprises water from the bulk of the ethanol product and unreacted acetic acid. - In the specific example, the initial column is operated to carry a small amount (preferably none) of acetic acid in the museum and a small amount (preferably none) of ethanol is infiltrated into the residue. The majority of the removal in the residue can vary with the composition of the crude ethanol product. The composition of the ethanol product is the result of the rate of acetic acid and the selectivity to ethanol. In a specific example, removing 90% of the water in the crude ethanol product from the residue, such as from 40 to 88% water or from 50 to 84% of the scale, removing less water from the residue may increase the museum. The acetic acid carried in the product. In addition, leaving too much water in the residue can also lead to an increase in ethanol in the infiltrated residue. Moreover, depending on the conversion rate, the energy demand may also increase when too much water is left in the product. Preferably, the major amount of water in the crude ethanol product fed to the column may be in the first residue, and the β is divided by, for example, removing up to about 90% of the water from the crude ethanol product and preferably. In some specific examples, the lower the acetic acid conversion and/or selectivity, the greater the water extract in the residue may be from 30% to 80%, such as from 4G% to 75%. - exemplify the frequency of the case towel 'this energy demand of the most tree of the hair of the hair of each of the 201245128 ethanol can be less than 5.6 million central heating units plus), such as less than 4.5 per gram of refined ethanol Million British thermal units (ΜΜβ^) or less than 35 million British thermal units (MMBtu) per ton of refined ethanol. In some embodiments, the process can be operated at higher energy requirements, provided that the total energy requirement is less than the removal of most of the water from the crude ethanol product from the distillate (eg, more than 65% removal from the crude ethanol product). ) the energy needed. Additional energy is required for the operation of the initial column to remove more water from the distillate and /f residue. When the water concentration in the distillate reaches an azeotropic amount, e.g., from about 4 wt% to about 7 wt%, the energy demand of the initial column may increase rapidly. In order to achieve these low water concentrations, it is necessary to increase the reflux ratio and result in an increase in energy demand for the column. For example, removing additional water and thus removing more than 9% of the water in the residue requires a reflux ratio of greater than 5:1, 咼:ι or higher than 3〇: reflux. This may result in additional energy requirements for the distillation column. The residue stream can comprise at least 85% acetic acid from the crude ethanol product, such as to; 90% and more preferably at least about 100%. When expressed in terms of the range, the residue stream preferably comprises from 85% to 1% by weight of unreacted acetic acid from the crude ethanol product, and more preferably from 9% to 100%. In one embodiment, substantially all of the unreacted acetic acid is recovered in the residue stream. By removing substantially all of the unreacted acetic acid from the crude ethanol product, in some instances, the process does not require further separation of acetic acid from the ethanol product. In this aspect, the ethanol product may contain a small amount of acetic acid, such as traces of acetic acid. The composition of the residue stream may vary with the acetic acid conversion as described below, as well as the composition of the crude ethanol product and the separation conditions in the first column. Depending on the composition, the residue stream may be: (i) recycled to the hydrogenation reactor in whole or in part, (ii) separated into an acid stream and a water stream, (iii) treated in a weak acid recovery process with a solvent. (iv) reacting with an alcohol to consume unreacted acetic acid, or (V) discarding it into a wastewater treatment plant. In another embodiment, it is also advantageous to remove ethanol from the recycle stream. This reduces the amount of ethanol to be passed through the catalyst and thus increases the ability to hydrogenate the carboxylic acid and/or ethyl acetate. A circulating stream comprising ethanol can be fed to the extraction separation unit to extract the ethanol and the raffinate can be fed to the reactor. The extracted ethanol can be mixed with the dried dehydrated ethanol obtained by separating from the water to increase the total recovery of ethanol. In one embodiment, at least 8% by weight of the recycled liquid stream is recovered and preferably at least 90%. Therefore, the total ethanol recovery can be greater than 9%, such as greater than 95 Å/〇. 201245128 The process of the present invention can be used with any hydrogenation process for making ethanol. Materials, catalysts, reaction conditions, and separation processes that can be used in the hydrogenation of acetic acid are detailed. The raw materials acetic acid and hydrogen used in the process of the present invention may be derived from any suitable source, including natural gas, petroleum, coal, and biomass materials. For example, acetic acid can be produced by methanolization, ethylene oxidation, ethane oxidation 'oxidative fermentation, and anaerobic fermentation. A methanol carbonylation process suitable for the manufacture of acetic acid is described in U.S. Patent Nos. 7,2,8,62,7,7,1,1,7,7,7,7,5,7,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5,5 The entire disclosure is incorporated herein by reference. Alternatively, ethanol production can be integrated with the sterol carbonylation process. As oil and natural gas prices become expensive or cheaper, methods for producing acetic acid and intermediates such as sterols and carbon monoxide from other carbon sources are gaining attention. In particular, it is advantageous to produce acetic acid from a synthesis gas ("syngas) derived from other available carbon sources when the petroleum is relatively expensive. For example, U.S. Patent No. 6,232,352, the entire disclosure of which is incorporated herein by reference A method of making a sterol plant for acetic acid. By improving the methanol plant, the significant cost associated with the production of carbon monoxide (CO) in a new acetic acid plant can be significantly reduced or substantially eliminated. All or part of the syngas is derived from decyl alcohol. The synthesis path is supplied to the separator unit to recover carbon monoxide, which is then used to make the acetic acid. In a similar manner, the hydrogen of the hydrogenation step can be supplied from the synthesis gas. In some embodiments, some or all of the above-described acetic acid hydrogenation processes are Part or all may be derived from syngas. For example, acetic acid may be formed from decyl alcohol and carbon monoxide, both derived from syngas. The syngas may be oxidized by reforming or steam reforming. Formed, and carbon monoxide can be separated from the syngas. Similarly, used in the step of hydrogenating acetic acid to form a crude ethanol product. Hydrogen can be separated from syngas. This syngas can be derived from various carbon sources. The carbon source can be selected, for example, from the group consisting of natural gas, gasoline, petroleum, coal, biomass materials, and combinations thereof. It can be obtained from bio-derived decane gas such as bio-derived gas produced by waste burial or agricultural waste. Biomass derived from fossil fuels such as coal or natural gas The syngas will have a detectable 14C isotope content. There will be a constant balance between constant new formation and constant decay degradation in the Earth's atmosphere 201245128, and the proportion of carbon atoms in the earth's air towel is constant for a long time. The survival of the system lies in the surrounding atmosphere, so the proportion of mc:12c in the same distribution ratio will stand in the living organism, and the distribution ratio will stop changing when the living organism dies, but 14C will decompose with a half-life decay of about 6000 years. The sterol, acetic acid and/or ethanol formed from the synthesis gas derived from the biomass material is expected to have a 14C content substantially similar to that of the living organism. For example, 'methanol, acetic acid and/or Or the i4c:12c&s example of ethanol may be one to a half of the C:12C ratio of the living organism to about 1. In other specific examples, the syngas, methanol, acetic acid and/or ethanol described therein are all derived from fossil fuels, That is, derived from 6〇, the carbon source produced by the year ago does not have a detectable 14C content. In another specific example, the acetic acid used in the hydrogenation step can be formed by fermentation of the biomass material. Preferably, the fermentation process utilizes an acetic acid production process or a homoacetogenic microorganism to ferment the sugar to acetic acid and produce a very small amount, if any, of carbon dioxide as a by-product compared to conventional yeast processes (generally With a carbon efficiency of about 67%, the carbon efficiency of the fermentation process is preferably greater than 7%, greater than 8%, or greater than 90%. Depending on the case, the microorganism used in the fermentation process is a genus selected from the group consisting of Clostridium, Lactobacillus, Moorella, Thermoanaerobacter, a group consisting of Propionibacterium, Propionispera, Anaerobiospirillum, and Bacteriodes, and especially the species selected from the group consisting of hyperthyroidism Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbrueckii, Propionibacterium acidipropionici ), a group consisting of Propionispera arboris, Anaerobiospirillum succinicproducens, Bacteriodes amylophilus, and Bacteroides ruminicola. 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 Application Serial No. 2008/0193989, the disclosure of which is incorporated herein by reference. Examples of biomaterials & include (but not limited to) agricultural waste, other cellulosic materials, wood residues in lumber yards, soft forests, and

Ϊ2 specifications pulp, corn, corn stalk, wheat L: ϊ ϊ Γ Γ animal waste, urban waste fertilizer, urban sewage, commercial f, _ juice stone, apricot kernel shell, large walnut shell, coconut shell 'ca coffee Touch, grass, cognac, wood paper, plastic cloth. Other raw noodles are straw black – iquor), which is an aqueous solution of lignin residues, semi-prime and domain chemicals. U.S. Patent Application Serial No. 5,377, 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 The process consists of hydrogenating a solid and/or liquid carbonaceous material to obtain a process gas which is lysed by other days of weaving. The syngas is converted to methanol which can be contacted to form 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 into syngas via gasification, and a general specification of 6,685,754 discloses a process for the manufacture of a composition of a ruthenium, such as a synthesis gas comprising hydrogen and carbon monoxide, which is incorporated herein. for reference. The acetic acid fed to the hydrogenation reactor also includes other carboxylic acids and anhydrides as well as acetaldehyde and acetone. Preferably, the suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These other compounds may also be hydrogenated in the process of the invention. In some embodiments, the presence of a carboxylic acid such as propionic acid or an aldehyde thereof may facilitate the production of propanol. Water may also be present in the acetic acid feed. Alternatively, the acetic acid in the vapor state can be obtained directly from the crude product in a flash vessel of the decyl alcohol carbonylation unit as described in U.S. Patent No. 6,657,078, the entire disclosure of which is incorporated herein by reference. For example, the crude steam product can be fed directly into the ethanol synthesis reaction zone of the present invention without the need to condense or remove water from acetic acid and light hydrocarbons, thereby saving overall processing costs. The acetic acid may be vaporized at the reaction temperature, and then the vaporized acetic acid may be fed in the undiluted state or with hydrogen diluted with a relatively inert carrier such as nitrogen, argon, helium, carbon dioxide or the like. The reaction in the vapor phase of the system, the temperature, should be controlled so that it does not fall below the dew point of the acetic acid. In one embodiment, acetic acid can be vaporized at a specific pressure at B. 201245128; at the point of flight, and then the acetic acid of the carrier is heated to the reactor inlet temperature. In another embodiment, the acetic acid is mixed with other gases prior to vaporization, followed by mixing and heating to the reactor inlet temperature. Preferably, the acetic acid is transferred to the vapor state by passing hydrogen and/or recycle gas through the acetic acid at a temperature of 125 C or below, and the combined gas stream is then heated to the reactor inlet temperature. Process for Hydrogenation of Acetic Acid to Form Ethanol Some specific examples may include various configurations using a fixed bed reactor or a 々IL bed reactor. In many embodiments of the invention, "insulation,", reactors, i.e., little or no internal conduits may be introduced into the reaction zone to add or remove heat. In other embodiments, a radial flow reactor (radial fl〇wreact〇r) or reactor groups may be utilized, or a set of reactors in series may be used, with or without heat exchange, quenching or introduction of additional reactors. Material. Alternatively, a shell and tubular reactor equipped with a secret transfer f can be used. In many instances, the reaction zone can be contained in a single vessel or in a tandem vessel having heat exchange therebetween. ^' In a preferred embodiment, a catalyst is used in a fixed bed reactor, such as a straight tube or a tubular reactor, where the generally gaseous reactant passes over or within the catalyst. Other reactors such as fluid or ebulent bed reactors (ebument bed rea_s) can be used. In some applications, the hydrogenation catalyst can be combined with an inert material to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant compound with the catalyst particles. The hydrogenation reaction can be carried out in the liquid phase or in the vapor phase. Preferably, the reaction is carried out in the vapor phase under the following conditions. The reaction temperature can range from a cavity to 35 〇t:, such as freely 叱 to 325C, from 225C to 300 ° C, or from 25 (TC to 300 ° C. The pressure can be from 1 kPa (kPa) to 3000 kPa. The range, for example, from 5 kPa to 23 kPa, or from 1 〇〇 kPa to 2 〇〇 pa kpa. The reactants can be fed into the reactor from a gas hourly space velocity (GHSV) of 50 hours. 1 to 50,000 hours-1. , such as from 500 hours - 1 to 30,000 hours ·!, from 1 hour · ^ 1 hour · ^ or from 1000 hours - 1 to 6500 hours - 1. Although the reaction per mole (four) consumes two Mohr-hydrogen is produced by molar hydrogen, but the actual molar ratio of hydrogen to acetic acid in the feed stream can vary from about 1 〇〇:1 to 1:1, as from 5〇:1 to 1:50, from 20:1 to 1:2, or from 18:1 to 2:ι. Contact or residence time can also vary widely, depending on various variables, such as the amount of acetic acid, - -11 - 201245128 catalyst , Reactor, Temperature, and Pressure. When a catalyst system is used instead of a fixed bed, the typical contact time ranges from a few milliseconds to over several hours, while the preferred contact time for at least the vapor phase reaction is from 0.1 to 100 seconds. Acetic acid The formation of ethanol is preferably carried out in the presence of a hydrogenation catalyst. Exemplary catalysts are described in U.S. Patent Nos. 7,608,744 and 7,863,489, and U.S. Patent Application Publication Nos. Nos. 2/01/0121114 and 2010/0197985, the entire contents of which are incorporated herein by reference. In another embodiment, the catalyst comprises a Co/Mo/S catalyst of the type described in U.S. Patent Application Publication No. 2009/0069, the entire disclosure of which is incorporated herein by reference. The catalyst may be a bulk catalyst. In a specific example, the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, iridium, platinum, chin, a group consisting of zinc, chromium, lanthanum, molybdenum and crane. Preferably, the first metal is selected from the group consisting of platinum, palladium, cobalt, nickel and ruthenium. As mentioned, in some specific examples, the catalyst Further included is a second metal which generally functions as a promoter. If a second metal is present, it is preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, rhodium, ruthenium. a group consisting of manganese, lanthanum, cerium, gold, and nickel. More preferably, the first metal is selected from a group consisting of copper, tin, indium, bismuth and nickel. The catalyst contains two or more metals, such as a first metal and a second metal, and the first metal is present in the catalyst. For the 仏丨 to (7) plus %, such as from 〇 1 to 5; ^ ^ 〇, or from 〇 1 to 3 wt Q / 〇. The second metal is preferably present in the range of 〇 1 to 2 〇 plus %, such as from 〇 1 to 10wt ° / 〇, or from 〇.1 to 7.5wt 〇 / 〇. Example of a preferred metal composition of the catalyst composition comprising platinum / tin, platinum / nail 'platinum / chain, put / 钌, palladium / ruthenium, cobalt /Palladium, Cobalt/Platinum, Cobalt/Chromium, Wrong/钌, //锡, 银/把,铜/把,铜/辞, 镇/把,金/纪,钉/铢, or 钌/铁. The catalyst may also include a third metal selected from any of the metals described above in the first metal or the second metal, as long as the third metal is the same as the first metal and the second metal. Preferably, the second metal is selected from the group consisting of diamond, radix, ruthenium, copper, zinc, turn, tin and antimony. When a third metal is present, the total amount of the third metal is preferably from 5 to 2% by weight, such as from 〇 i to i 〇 wt%, or from ι to 7.5 wt%. - Specific wealth, contact with the package, tin and Syria. In some specific examples of the invention, in addition to one or more metals, the catalyst further includes a •12-201245128 support or a modified support (modifled supp〇rt). The term "reformation carrier" used in this article refers to the burden of containing (4) materials and gall bladder materials. The total weight of the support or the modified support is based on the total weight of the catalyst, preferably _%, such as from 78 to 97% by weight, or from 5% by weight. Preferably, the body comprises a restraining body such as cerium oxide, oxidized stone cerium/oxidized sulphate, group IIA sulphuric acid salt such as sulphuric acid sulphate, pyrolytic oxidized sphincter, high tonnage oxidized stone cerium and its age. No prison can contain (material) oxygen, oxidized titanium, oxidized, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbon and pot mix. The support may be modified (4) and (4) modified, present in an amount of 0.1 to 50% by weight based on the touch weight 2, such as from 0.2 to 25 wt%, from 3 to 5% by weight, from 3 to i5 wt%. In some specific examples, the bulk modifier may be an acidic modifier that increases the acidity of the catalyst. Suitable acidic support modifiers can be selected from the group of gold oxides, oxides of the anode metals, oxides of the Group VIB metals, oxides of the VIIB metals, oxides of the metal compounds, purified substances and their ages. Group group. The acid carrier is changed into a group consisting of f, Z, R2, Q2, P, M, (10), and 峨 by %03, α·203, V205, Mn02, CuO, C〇2〇3, and Bi2〇3. Preferred support modifiers include oxides of cranes, molybdenum and niobium. In the other eight embodiments, the bulk modifier may be an inert modifier having low or no volatility. This qualitative modification is as simple as (i) soil metal oxide, (8) metal oxide, (111) soil metal bismuth citrate, (iv) alkali metal bismuth citrate, (ν) ΠΒ Group of metal oxides, (νι) steroid metal metasilicate, (vii) Group IIIB metal oxide, (viii) mB metal bismuth citrate and mixtures thereof. The alkaline support modifier may be selected from the group consisting of sodium, potassium, magnesium, calcium, ruthenium, ruthenium and any of the oxides and metasilicates and any of the foregoing oxides. In one embodiment, the alkaline modifier is calcium citrate such as calcium metasilicate (CaSi〇3). Calcium metasilicate can be crystalline or amorphous. The catalyst on the modified support may comprise one or more metals supported on the ruthenium oxide support, which are selected from the group consisting of platinum, palladium, azurite, tin and antimony, and may optionally be borrowed The group selected from one or more modifiers is modified by a group of metaphysic acid dances and one or more oxides of tungsten, molybdenum and/or vanadium. The catalyst composition suitable for use in the present invention is preferably formed by metal saturation (metal • 13-201245128 impregnation) in a modified support. However, other processes such as chemical vapor deposition may also be used. The immersion technique is described in the aforementioned U.S. Patent Nos. 7,608,744 and 7, 863, 489, and U.S. Patent Application Publication No. 2010/0197485, the entire disclosure of which is incorporated herein by reference. After the catalyst is washed, dried and calcined, the catalyst can be reduced to activate the catalyst. The reduction is carried out in the presence of a reducing gas, preferably hydrogen, "5. The reducing gas is continuously passed through the catalyst at an initial temperature to which it is increased. In one embodiment, the reduction is preferably carried out after the catalyst is loaded in a reaction vessel to be hydrogenated. In particular, the hydrogenation of acetic acid achieves an advantageous conversion of acetic acid and an advantageous selectivity and yield of ethanol. For the purposes of the present invention, the term "conversion" means the amount of acetic acid in the feed to a compound other than acetic acid. The conversion is expressed as a percentage of acetic acid in the feed. The conversion can be as little as 40%, such as At least 5G%, at least 60%, at least 7G% or at least 8G%. Although a catalyst with a south conversion rate is more desirable, such as at least secret or at least generous, in some specific cases, low conversion to high selectivity for ethanol The rate of the catalyst is acceptable. The selectivity is expressed as the percentage of the converted sigmoid. It should be understood that the conversion from the acetic acid has an independent selectivity and the selectivity and conversion are independent of each other. 6. The acetic acid is converted to ethanol, which is called % of the conversion of ethanol. The catalyst selectivity for ethanol is at least 6G%, such as at least 7G%, or at least 80%. The surface to be transferred has a pouring material, such as granules and sulphur tS! The selectivity of the undesired products is preferably less than 4%, such as less than 2 〇 /. or 〒" means based on the weight of the catalyst used per hour. In the nitriding period catalyst / hour. Such as the grams of ethanol. Productivity can range from 100 to 3, gram of ethanol per kilogram of carbon. °3 such as s pain, _, _ ' ug, ship and dioxide 201245128 Table 1: crude ethanol product composition concentration (wt.%) concentration (wt.%) concentration (wt·%) concentration (wt.% Ethanol 5 to 72 15 to 72 15 to 70 25 to 65 acetic acid 0 to 90 0 to 50 0 to 35 0 to 15 water 5 to 40 5 to 30 10 to 30 10 to 26 ethyl acetate 0 to 30 1 to 25 3 To 20 5 to 18 acetaldehyde 0 to 10 0 to 3 0.1 to 3 0.2 to 2 other 0.1 to 10 0.1 to 6 0.1 to 4 In a specific example, the crude ethanol product of Table 1 may have a low concentration of acetic acid but a high conversion ratio, And the acetic acid concentration may range from 0.1% by weight to 20% by weight, such as 〇.〇5wt% to 15wt%, O.lwt0/. Up to 10wt. /. 'or lwt% to 5 wt%. In a specific example having a lower amount of acetic acid, the acetic acid conversion is preferably greater than 75% 'e.e., greater than 85% or greater than 90%. In addition, the selectivity to ethanol is also relatively high ' and preferably greater than 75%, such as greater than 85°/. Or greater than 90%. Ethanol Recovery An exemplary ethanol recovery system according to a specific example of the present invention is shown in Figures 1 and 2. Each hydrogenation system 100 provides a suitable hydrogenation reactor for the specifics of the invention and a process for separating the hexanol from the crude reaction mixture. System 1 includes a reaction zone 101 and a separation zone 1〇2. The reaction zone 101 includes a reactor 103, a hydrogen feed line 1〇4, and an acetic acid feed line 1〇5. Separation zone 1〇2 includes separator 106, distillation columns 1〇7 and 115, and water separation unit 12. Figure 2 also provides extractor 128 for reducing the concentration of ethanol recycled to reaction zone 101. Hydrogen and acetic acid are fed to vaporizer 108 via lines 104 and 105, respectively, and a vaporized n. feed stream is produced in line 1〇9, which is directed to reactor 1〇3. In a specific example, the pipelines 1〇4 and 1〇5 can be combined to feed the vaporization_8. The airflow and flow temperature in tube_9 is better than l〇〇°C to 35〇°C, such as from 12〇. (: to 3HTC or as self-contained. Any feed that has not been steamed is removed from the vaporizer 1〇8 and can be recycled or discarded. In addition, although the pipeline, 1〇9 is shown as being guided by the reaction||1_ The end, but the tube_9 can lead to the side, upper or bottom 4 of the reactor. Further modifications and additional components for the reaction H〇1 and the separation zone 102 are described as -15-201245128. The reactor 103 contains ribs. In the case of a hydrogenation of a ship, preferably a catalyst for hydrogenating acetic acid, one or more guard beds (guard bedsX not shown) may be used upstream of the reactor 103 to protect the catalyst from contact with the feedback/ The impurities contained in the Wei dynasty or the impurities of the magnetic thief. This protective bed can be used in aviation or liquid inspection. Suitable protective bed materials include, for example, carbon, oxygen cutting, oxidation, shouting or lion. In a certain state, The guard bed medium is functionalized (fUncti〇nalized), such as functionalized with silver to capture a specific species such as sulfur or it is subjected to a hydrogenation process, and is extracted from the reactor 1〇3 via line (10) (preferably continuously withdrawn). The crude ethanol product in line 110 can be condensed and fed to the separator. 1〇6, which in turn forms a vapor stream 111 and a liquid stream 112. The suitable separator 106 can include a flasher or a liquid separator. Separator 1〇6 can be operated at temperatures from 2 °C to 250 °C, such as from 30 °C to 225 °C or from 60 °C to 200 °C. The pressure of the separator 1〇6 can be from 5〇妓& to 25〇〇 sand&, such as from 75kPa to 225〇kPa or from l〇〇kPa to 2i00kPa. Optionally, the crude ethanol product in line 11 can be passed through one or more membranes to separate hydrogen and/or other non-condensable gases. The vapor stream hi flowing from the separator 106 may include hydrogen and hydrocarbons, and may be purged and/or returned to the reaction zone 1〇. As shown, the vapor stream hi is combined with the hydrogen feed. Vaporizer 108. In some embodiments, the returned vapor stream lu can be compressed prior to being combined with the hydrogen feed \〇4. The liquid stream 112 from separator 106 is withdrawn and pumped into the side of distillation column 107 (also referred to as the "acid separation column"). In one embodiment, the contents of liquid stream 112 are substantially similar to the crude ethanol product obtained from reactor 103, but the composition is substantially free of hydrogen, carbon dioxide, helium or sulphur, which is a fine separator 106. Remove. Accordingly, liquid stream 112 can also be referred to as a crude ethanol product. Exemplary components of liquid stream 112 are provided in Table 2. It should be understood that liquid stream 112 may contain other components not listed, such as components derived from the feed. 201245128 Table 2: Tower feed composition (liquid stream 112) Concentration iwt.%) Concentration (wt·%) Concentration (wt.%) Ethanol 5 to 72 10 to 70 15 to 65 Acetic acid < 90 5 to 80 〇 to 35 Water 5 to 40 5 to 30 10 to 26 ethyl acetate < 30 1 to 25 3 to 20 acetaldehyde < 10 0.001 to 3 0.1 to 3 acetal < 5 0.01 to 5 0.01 to 3 acetone < 5 0.0005 to 0.05 0·001 to 〇〇3 Other esters <5 < 0.005 < 0.001 Other ethers <5 <5 < 0.005 < 0.001 __lethastanol----- < 0.005 A < 0.001 The amount indicated by less than (<) in the entire specification table is preferably absent or, if present, greater than 0.01% by weight. The "other esters" in Table 2 may include, but are not limited to, ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate or a mixture thereof. In Table 2, other ethers may include, but are not limited to, diethyl ether, methyl ethyl ether, isobutyl ethyl hydrazine or a mixture thereof. The "other alcohols" in Table 2 may include, but are not limited to, decyl alcohol, isopropanol, n-propanol, n-butanol or a mixture thereof. - In particular embodiments, the liquid stream 112 may include propanol such as isopropyl alcohol. The amount of alcohol and/or n-propanol is from 0.001 to 0.1 wt%, from 0.001 to 0.05 wto/〇, or from 〇ooi to 〇.〇3 wt%. It should be understood that these other components may be contained herein. Any distillate or residue stream is described and will not be described herein unless otherwise indicated. Optionally, the crude ethanol product in line 110 or liquid stream 112 can be fed to the acetification reactor, hydrogenolysis reaction. The esterification reactor can be used to consume acetic acid present in the crude ethanol product to further reduce the amount of acetic acid to be removed. Hydrogenolysis can be used to convert the ethyl acetate in the crude ethanol product to ethanol. It can be introduced into the middle portion of the first column 107, in the following half or in the middle three points. In one specific example, 'entrainers' are not added to the column. In the first column 107, water and unreacted Acetic acid is combined with any other heavy components (if present) from the liquid •17- 201245128 Stream 112 It is removed and withdrawn as a residue in line 113 (preferably continuously withdrawn). The first column 107 also forms an overhead which is condensed out of line 114 and is for example, from 1 〇:1 to 1.10, as The ratio is from 3:1 to 1:3 or from 1:2 to 2:1. In a specific example, it is preferred to operate at a reflux ratio of less than 5:1. The column 107 is operated at about 10 kPa. The temperature of the residue flowing out of line 113 is preferably from 9 (TC to 13 (TC, such as from 95 ° C to 12 (TC or from 10 (TC to 115). The bottom of the crucible 107 is maintained at a relatively low temperature to extract including A residue stream of both water and acetic acid, thereby providing an energy efficiency advantage. The temperature of the distillate flowing out of line 114 is preferably from 6 〇〇c to 9 (rc, such as from 65 ° C to 85 ° C Or from 7Gt to 8 (TC. In some specific examples, the pressure of the first column 1Q7 may range from 0.1 kPa to 510 kPa, such as from ikpa to 475 kPa or from the cell to 375 kPa. Exemplary components of the composition of the compositions are shown in Table 3. It should also be understood that the spills and residues may also contain other components not listed, such as components derived from the feed. For convenience, the first column 107 Distillate Residues may also be referred to as, the first distillate, or, the first residue - other towers - annihilation (four) may also be table (iv) similar number modification (such as the second 'third, etc.) to distinguish each other 'But this modification should not be interpreted as requiring any particular separation order.

-18· 201245128 Table 3: First Tower 107 Concentration (wt.%) Concentration (wt·%) Concentration (Wt.0/o) Distillate Ethanol 20 to 90 30 to 85 45 to 85 Water 4 to 38 7 to 32 7 to 25 acetic acid < 0.5 0.001 to 0.5 〇. 〇 1 to 0.5 ethyl acetate < 60 5 to 40 8 to 45 acetaldehyde < 10 0.001 to 5 0.01 to 4 acetal < 4.0 < 3.0 < 2.0 propyl I < 0.05 0.001 to 0,03 〇.〇1 to 0.025 Residual acetic acid <90 1 to 50 2.5 to 40 water 30 to 100 45 to 90 60 to 90 ethanol <1 <0.9 <0.5 In a specific example, the acetic acid in the residue may be less than 3 wt%, such as from 0.5 to 3 wt% or from 1 to 2. wt%, at a conversion of 90%. And the water concentration in the residue at a low conversion of less than 5% can be less than 3 〇 wt 〇 / 0, or less than 2 〇 wt%, while the concentration of acetic acid in the residue can be greater than 40 wt%, such as More than 6〇wt% or more than 8〇wt%. Some species, such as acetals, can be decomposed in the first column 1〇7, leaving a very small amount of acetal or even no detectable amount of acetal in the distillate or residue. In addition, an equilibrium reaction between acetic acid and ethanol or ethyl acetate and water may occur after the crude ethanol product has flowed out of the reactor 103. Depending on the concentration of acetic acid in the crude ethanol product, this equilibrium can be driven to ethyl acetate. This reaction can be adjusted using the residence time and/or the temperature of the crude ethanol product. Depending on the amount of water and acetic acid contained in the residue of the first column 107, the line 113 may be subjected to one or more of the following processes for the treatment of the fourth step of the first step of the residue, and The concentration of acetic acid can be set to any process. When the #_ residue comprises mainly indole acetic acid, such as more than 70% by weight, the residue may be recycled to the reactor 1〇3 without having to be dehydrated. When the residue includes a major amount of acetic acid, for example, the residue The material can be separated into an acetic acid liquid stream and a water liquid stream. Some specific examples can be recovered from the first residue having a low acetic acid concentration of -19-201245128. The residue can be separated into an acetic acid stream and a water stream by a distillation column or one or more membranes. If a membrane or array of membrane arrays is used to separate acetic acid from water, the membrane or array of membrane arrays can be selected from any suitable acid resistant membrane that can be removed from the permeate stream. The resulting acetic acid liquid stream is returned to the reactor 103 as the case may be. The resulting aqueous stream can be used as an extractant or to hydrolyze an acetal- or ester-containing stream in a hydrolysis unit. In other embodiments, for example, when the residue in line 113 comprises less than 5% by weight of acetic acid, possible options include one or more of the following: (7) returning a portion of the residue to reactor 103, (ii) neutralizing Acetic acid, (iii) reacting acetic acid with an alcohol, or (iv) discarding the residue in a wastewater treatment plant. It is also possible to use a weak acid recovery solvent in which a solvent can be added (as the case may be an azeotropic agent) to recover the residue comprising less than 5 Gwt% of acetic acid. (IV) μ. Examples of the solvent include acetic acid, propyl acetate, and isopropyl acetate. g, acetic acid butyl vinegar, acetic acid ethyl acetate, monopropyl ether, carbon disulfide, tetrahydrofuran, isopropanol, ethanol and c3_Cu burning. When neutralizing acetic acid, it is preferred that the residue in the line comprises less than 1% by weight of acetic acid. The acetic acid can be neutralized by any suitable metal or soil test such as sodium hydroxide or potassium hydroxide. When acetic acid is used, it is preferred that the residue (four) comprises less than 5 Qwt. /. Acetic acid. The alcohol can be any suitable alcohol such as methanol, ethanol, propanol, butanol or mixtures thereof. The reaction forms vinegar which can be integrated with the system, such as manufacturing or manufacturing processes. Preferably, the alcohol comprises ethanol and the acid comprises (10). Optionally, the obtained vinegar can be fed to the hydrogenation counter. In some specific examples, when the residue includes a very small amount of acetic acid, such as less than 5% by weight, the residue is discarded in the wastewater treatment without further treatment. The organic matter in the residue and the total acetic acid end product can be advantageously applied to microorganisms in a sanitary wastewater treatment plant. The s-line 1 Μ 之 之 之 较佳 较佳 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇In addition, the acetic acid in the 'London' contains no acetic acid for the substance B, and if it is contained, it is only a very small amount of acetic acid. Any test can be included. The desired separation and/or purification function °, ,, α tower preferably includes from 1 to 150 plates, such as from 1 to 1 plate number, • 20 to 201245128 from 20 to 95 plates or from 30 to 75 plate number of trays (tray c〇iumn). The plate may be a sieve plate, a fixed valve plate, a movable valve plate or any other suitable design known in the art. In other embodiments, structured packing may be used. Or a randomly packed packed column. The trays or packing may be arranged in a continuous column or may be arranged in two or more columns such that steam from the second stage enters the second At the same time, the liquid from the second stage enters the first stage, etc. The relevant condensers that can be used with each distillation column and The liquid separation vessel can be any conventional and simplified in the drawings. Heat can be applied to each column substrate or to the circulating bottoms stream via a heat exchanger or reboiler. Other types of reboilers can be used, such as internal Boiling. The heat supplied to the refill can be derived from any heat generated during the integration process with the reboiler, or from external sources such as other hot chemical processes or reboilers. In the drawings, a reactor and a side steamer are shown, but in the various embodiments of the invention, additional reactions s mu, condensation n, heating elements and other components may be used. It is known that various condensers, pumps, Compressors, reboilers, rollers, compartments, connectors, two-way containers, etc., which are used for chemical processes, can also be combined and used in the process of the present invention. The temperature and pressure used in the tower can be changed. In the upper operation, a pressure of 10 kPa to 3000 kPa is generally used in the _ area, but in some specific examples, the sub-atmospheric pressure or the super-atmospheric pressure may be utilized. The temperature in each zone is generally used as a composition to be removed as a postal item and Remove residue for residue The range of the boiling point of the composition. As is well known in the art, the temperature of the mosquitoes in the operation of the mosquitoes is touched (4) and the pressure of the test is pressed. In addition, the feed rate can be determined by the size of the manufacturing process. And if it is described, it is generally referred to as the feed weight ratio. The contents of the library in Figure 2: 14 include ethanol, water and other organic substances such as ethyl acetate and/or ethyl acetate. In some specific examples, The composition of the museum may have a selectivity rate of, for example, greater than 90 〇 / 〇, greater than 95% or greater than 97%. The amount of water in the pipeline may be close to that of water (four), such as the formation of ethanol / water = 4 wt%, preferably less than 20 wt%, such as less than 12 tree% or less than 75 percent. ^ Depending on the desired route, it may be better to remove water from the f_garment. € • 21 · 201245128 ^ Some specific examples 'Removed virtually all of the water to produce an anhydrous B, product suitable for burning. Water can be removed from the museum in line 114 using different separation techniques. The best technique involves the use of a display tower '- or Dona, one or more adsorption units or a combination thereof. Although the feed in line 1M of Fig. 1 mainly includes ethanol and water, in the present invention, the health products in the 'f line 114 may further include ethyl acetate and ethylene. As shown in the figure, the second tower 115 (also referred to as "light hydrocarbon tower (11 § 1 ^ 11 as (; 〇 11111111)") can remove acetic acid from the museum in the pipeline 114 and B Specifically, the column 11S produces a light-weight product including ethyl acetate and ethylene in the line 116, and produces an ethanol residue including ethanol and water in the line 117. "In Fig. 1, the line 114 is used. The second museum 115 may be a plate tower or a packed tower. The second tower 115 may be a plate tower or a packed tower. In a specific example, the second portion is introduced into the second tower 115. The tower can be a plate-like tower having a number of plates of 5 to 7 G, such as from 15 to 50 plates or from 20 to 45 plates, when the tower is used in a tower with a number of towers, without water extraction. Preferably, the line 114 is introduced to the second plate. ° The light hydrocarbon column (1) may be scaled to a fine column, as appropriate. Suitable extractants may include, for example, dimethyl, glycerol, diethylene glycol, m. Hydrogen, hydrazine, hydrazine, dimethyl dimethylamine, 1,4-butanediol, ethylene glycol pentanediol, propylene glycol, tetraethylene glycol-polyethylene glycol, glycerol-propylene glycol Alcohol from Ding Er , diethyl ether, formic acid, brewing, argon, hydrazine, hydrazine, dimercapto, propylenediamine, hydrazine, hydrazine, dimethylethylenediamine, diethylenetriamine, hexamethylenediamine, and , 3 · diamine based sister, thiol light, twelve burning, thirteen burning, fourteen courtyard, chlorinated stone «the combination. In addition, the extractant can be an aqueous liquid stream including water. If the extractant includes Water's water can be obtained from an external source or from an internal material return/recirculation line of one or more other towers or water separation units. By f, the extraction_feeder is higher than the outlet of the pipeline ιΐ4, the entry point. When extracting _, it is appropriate to scream for extra steaming to remove the extractant and to circulate the extractant. Although the temperature and pressure of the second column 115 are variable, when running at about 2 至 to 7 咖The temperature of the second material flowing out in the line 117 is preferably self-contained to 35 C to or from 40 ° C to 65. The temperature of the second library flowing out of the line 116 is preferably from 20 C to 55. 〇 ' as from 25 (: to 5 (TC or thief to machine. Second tower! 15 can be operated in the vicinity of 22-201245128 or under reduced pressure under vacuum to further facilitate the division Ethyl acetate and ethanol. In one embodiment, the pressure of the second column 115 can be in a range from, for example, from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. An example of the composition of the distillate and residue of the second column 115 The components are shown in Table 4. It should be understood that the distillate and the residue may also contain other components not listed, such as components derived from the feed. Second distillate ethyl acetate acetaldehyde ethanol water second residue Ethyl alcohol water ethyl acetate acetic acid Table 4: Light hydrocarbon column 115 concentration (wt·%) concentration (wt%, 5 to 90 < 60 < 45 < 20 40 to 99.5 < 60 < 1 < 0, 5 10 to 80 15 to 75 1 to 40 1 to 35 0.001 to 40 0.01 to 10 50 to 95 〇·〇1 to 35 0.1 to 5 60 to 90 0.1 to 30 0.001 to 2 < 0.01 0.001 to 0.5 0.001 to 0.01 The ethanol in the residue is preferably at least 2_1 'e. to 45. at least 8 • at least (four) or at least 15:1 for the weight of ethanol in the second library. Preferably, the weight ratio of the second residue in the second residue of acetic acid is less than Q7: if the ratio is less than 〇·2:1 or 0.1, it should be understood that when the extractant is used, the residue The composition will also include the extractant. Preferably, the second residue comprises less than Q (1% by weight of acetic acid and also less than 35 liters of water. The water separation unit 121 shifts the remaining water first residue. In some specific examples, it may be desirable to have steam fed to the water separation unit. Better: What can be made:? The vapor portion of the ethanol residue in the ethanol residue in line 117 of the gas can be introduced into the water separation motion = • °S more ethanol ethanol product stream 123. The water separation unit can remove at least 90% water from the treated portion of the 23·201245128 ethanol residue in line 117, and more preferably from 95% to 99.99%. In one embodiment, the ethanol product stream 123 has a lower water content than the ethanol residue in line 117. The ethanol product stream 123 can include less than 8 milk% water, such as less than 4% water, less than 3 wt% water, or less than 1 wt% water. Preferably, at least 95% of the ethanol from the ethanol residue in line 117 is recovered by the water separation unit 121 in the ethanol product stream 123, and more preferably at least 99. /. Ethanol. The aqueous stream 122 can be mixed with any aqueous stream from system 100 and is preferably removed from the system. The aqueous stream may also include ethanol, in which case it may be desirable to feed all or part of the aqueous stream back to column 115 for further ethanol recovery. The water separator 121 may be an adsorption unit, a membrane, a molecular sieve or a combination thereof. When a membrane is used, it can be a membrane array set to remove water. In one embodiment, the adsorption unit can be a pressure swing adsorption (PSA) unit. The PSA unit can be operated at a pressure from 3 (yt to 160 ° C, such as from 80 ° C to 140 ° C and from o. oikpa to 55 kPa, such as from 1.3 to 150 kPa. The PSA unit Two to five beds may be included. Depending on the type of water separator 121, it may be desirable to compress the vapor portion of the ethanol residue in line 117. Compression may be necessary especially when using a membrane. Including acetic acid and/or ethyl chain The second take-up in line 116 preferably reflows as shown in Figure 1 'e. For example, a reflux ratio of 1:30 to 30:1, such as from 1:5 to 5:1 or from 1:3 The reflux ratio of 3:1 is refluxed. On the one hand, it is not shown, but the second distillate or a part thereof can be returned to the reaction H1G3. There is a specific example +, and a part of the first work is returned to the reactor 103. It is possible that the acetic acid acetonitrile / or the ethylene material in the advantageous H product is further reacted in the gasification reactor 103 or the secondary reactor 。r. The effluent from the secondary reactor can be fed into the reactor. In 103, additional ethanol is produced, or fed to a steaming tower such as column 1 or 7 or 115 to recover additional ethanol. In some specific examples, the second distillate in the official line 116 Can include up to 12% by weight of water. All or part of the second distillate on the right is returned to the reactor 1〇3, which must be removed from the line ιΐ6. It can be, for example, by unit, or multi-faceted, molecular sieve, extraction steaming Or a combination thereof removes water from the second library in line 116. In some embodiments, an adsorption unit may also be used to remove water from the second library in line 116, resulting in less than 1 wt% water. And more preferably less than 0.5wt 〇 / 〇 water distillate. 201245128, - in the specific case 'flow of the pipeline and containing 6 acid (four) read stream. This can make it contain or reduce the acid & vinegar The liquid is circulated to the reaction H1G3 towel to remove other impurities. The purification purge stream may have a value as a source of ethyl acetate and/or acetic acid. As shown in Fig. 2, the second library in the line 116 is fed. The human extraction unit 128 recovers hexanol and reduces the concentration of ethanol recycled to the reaction ϋ1〇3. The extraction unit can be a multi-stage extractor. In the extraction unit 128, the second effluent is fed together with at least one extractant 1S9 In one embodiment, the extractant 129 can be benzene, propylene glycol, and cyclohexane. Water is used, but the extractant 129 preferably does not form an azeotrope with ethanol. The preferred extractant 129 is preferably non-carcinogenic and non-cracking. Preferably, the extractant 129 is from the second museum. Extracting Ethanol^ Extract 130 The extractant 129 can be recovered from the column 131 and returned via line 13. The ethanol in line 132 can be mixed with the ethanol product stream 123. In one embodiment, the raffinate 133 comprises Less than 2 wt% ethanol 'e.g. less than 1 plus/or ethanol or less than 5 wt% ethanol. Raffinate 133 can be returned to the reaction zone ιοί. Preferably, the raffinate I% is less ethanol than the second distillate in line 116. In some embodiments, at least a portion of the raffinate 133 and/or at least a portion of the extract from the line 130 can be washed out of the system. The range of completed ethanol compositions is shown in Table 5 below. Component Table 5: Concentration (wt.%) Completed ethanol composition concentration (wt.%) Concentration (wt.%) Ethanol 75 to 99, 5 80 to 99.5 85 to 99.5 Water <12 0.1 3. 9 0.5 to 8 Acetic acid <1 < 0.1 < 0.01 ethyl acetate < 2 < 0.5 < 0.05 acetal < 0.05 < 0.01 < 0.005 propylene I < 0.05 < 0.01 < 0.005 isopropyl alcohol < 0.5 < 0.1 < 0.05 n-propanol < 0.5 < 0.1 < 0.05 The finished ethanol composition of the present invention preferably contains a very small amount, such as less than 0.5% by weight of other -25-201245128, such as methanol, butyl Alcohol, isobutanol, isoamyl alcohol and other C4_C2 sterols... In the specific example, the amount of isopropanol in the ethanol composition of Yuancheng is from the surface, and the weight of the surface is increased from QSiUOOOwppm, from Qing to 7〇. 〇 wppm, or from 15 〇 to 5 〇〇 wppm. In one embodiment, the finished ethanol composition is substantially free of (d), and optionally includes less than 8 stalks, such as less than 5 wppm or less than iw ppm. Some of the ethanol products may flow as a liquid from the water separation unit (4) described above when the veins are separated. The ethanol concentration of the ethanol product may be higher than that shown in Table 5, and is preferably greater than 97% by weight of ethanol, such as greater than 98% by weight or greater than 99%. The ethanol product in this aspect preferably comprises less than 3 wt% water, such as less than 2 or less than 0.5 wt%. The finished ethanol composition of the present invention can be used for various purposes, including as a fuel, solvent, chemical raw material, pharmaceutical product, detergent, disinfectant, nitrogen transport or 11 consumption. In the case of fuel, the ethanol composition of the product can be used in combination with gasoline for vehicles such as automobiles, boats and small pistons. In the course of the _ 顾 途 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The finished product can also be used as a processing solvent in the manufacturing process of pharmaceutical products, food preparations, dyes, photochemicals and latex processing. < The completed ethanol composition can also be used as a chemical raw material to manufacture other chemicals such as vinegar, acrylic acid, ethyl acetate, ethylene, glycol oxime, ethylamine, chain, H-based alcohol, especially Said. An acetic acid (five) towel is produced, and the finished ethanol city can be esterified by B=. In other applications, the finished ethanol composition can be dehydrated to produce ethylene. Any of the known dehydration catalysts can be used to dehydrate the ethanol, as described in the unexamined U.S. Patent Application Serial No. 2010/0030002, the entire disclosure of which is incorporated herein by reference. For example, a zeolite catalyst can be used as the dehydration catalyst. Preferably, the zeolite has a pore diameter of at least about 0.6 mn, and preferably the zeolite comprises a dehydration catalyst selected from the group consisting of mordenite, ZSM-5, ruthenium and iridium. Zeolite X is described, for example, in U.S. Patent No. 2,882,244 and the disclosure of U.S. Patent No. 3,13, the entire disclosure of which is incorporated herein by reference. Rifengwen is provided to make the invention disclosed herein easier to understand. Should understand this

-26- 201245128 Example f is an outline and should not be considered as any way to detain the invention. It is obvious that the improvement of the spirit and scope of the present invention will be apparent. In addition, it is to be understood that the subject matter of the invention and the various specific embodiments and various features described herein may be combined or interchanged in whole or in part. In the foregoing description of the specific examples, the specific examples of the other specific examples may be appropriately combined with - or a plurality of other specific ones, which are well known to those skilled in the art. The invention is illustrated and not intended to limit the invention. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be more fully understood from the following description of the embodiments of the invention. Fig. 1 is a schematic view showing an ethanol production system having a water separation unit to separate organic impurities after a distillation column according to an embodiment of the present invention. Figure 2 is a schematic illustration of an ethanol manufacturing system for reducing ethanol concentration in a circulating liquid stream in accordance with one embodiment of the present invention. [Main component symbol description] Code description 100 Hydrogenation system 101 Reaction zone 102 Separation zone 103 Reactor 104 Hydrogen feed line / line 105 Acetic acid feed line / line 106 Separator 107 First tower • 27- 201245128 Code description 108 Vaporizer 109 Line 110 Line 111 Steam stream 112 Liquid stream 113 Line 114 Line 115 Light hydrocarbon column / Second column 116 Line 117 Line 121 Water separation unit 122 Water stream 123 Ethanol product stream 128 Extractor 129 Extractant 130 Extract 131 Recovery tower 132 Pipeline 133 Raffinate -28-

Claims (1)

201245128 VII. Patent Application Range: 1. A process for producing ethanol, comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form a crude ethanol product; and partially purifying the crude product in the column. The ethanol product is separated into a first distillate comprising ethanol, ethyl acetate and at least 5 wt/hr of water, and a first residue comprising acetic acid and water, wherein a majority of the water is fed to the crude ethanol product of the column. Removed from the first residue; separating at least a portion of the first distillate into a first liquid stream comprising ethanol and water and a second liquid stream comprising ethyl acetate; and removing the single The first liquid stream removes water to form an ethanol product stream, and the strip is not moved from the first item before the at least part of the first substance is separated. 2. The process of the first item of the patent range, wherein 30 to 9 % of the water in the crude ethanol product is removed in the first residue stream. As stated in the aforementioned patent application, (10)% by weight of ethyl acetate. The process of any of the preceding claims, wherein the second residue comprises less than wt% water. The process of the item wherein the second residue comprises less than 35 water content as low as any of the residues of the preceding claims. The process of the present invention, wherein the ethanol product stream has a process according to any one of the preceding claims, wherein the ethanol product stream comprises less than -29. 11.201245128 12. 13. 14. 15. A process according to any of the preceding claims, which further comprises recovering acetic acid from the first residue and returning at least a portion of the recovered acetic acid to the reactor. 4% by weight of water. A process according to any one of the preceding claims, wherein the acetic acid is formed from methanol and carbon monoxide, wherein the sterol, the carbon monoxide and the hydrogen of the hydrogenation step are derived from a syngas, and wherein the syngas is derived from A carbon source selected from the group consisting of natural gas, oil, petroleum, coal, biomass materials, and combinations thereof. The process of claiming the scope of the patent, wherein the first residue comprises 〇.5(tetra)acid' the process further comprises neutralizing or reacting the acetic acid in the first residue, which in turn includes the (four) portion The process of the === item, which in turn includes extracting the second "object 5^ * 3〇·