TW201204695A - Process for separating acetaldehyde from ethanol-containing mixtures - Google Patents

Abstract

Purifying and/or recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid. Separation and purification processes of crude ethanol mixture are employed to allow recovery of ethanol and remove impurities. In particular, light ends are separated in an acetaldehyde removal column operating at a pressure greater than atmospheric pressure to recover acetaldehyde that may be returned to the reactor and reduce acetaldehyde concentrations in an ethyl acetate stream.

Description

201204695 Code Description 225 Pipeline V. In this case: When there is a chemical formula, please disclose the chemical formula that best shows the characteristics of the invention: VI. Description of the invention: Priority claim The claim of the present invention is based on the April 2nd issue of 2〇n U.S. Patent Application Serial No. 13/78,754, U.S. Patent Application Serial No. 269, filed on Jan. 6, s. The entire content and disclosure are incorporated herein by reference. ^ [Technical Field to Be Invented by the Invention] The present invention is generally related to Langmu and/or ethanol, and _ is a bismuth from the age of B. [Prior Art] = The conventional ageing formula for ethanol is derived from petrochemical supplements, such as: petroleum, natural gas, and coal repellency from feed intermediates such as syngas or starchy feedstocks or cellulosic feedstocks, for example. The traditional method for producing ethanol is derived from petrochemical feedstocks, as well as cellulose II, ethylene-catalyzed hydration, methanol homologation, direct alcohol synthesis, and i^rr_Tropsch synthesis. The price of unstable petrochemical raw material materials will cause fluctuations in the cost of ethanol production. When the price of raw materials rises, the demand for the production of ethanol will increase. The starch material and the cellulose shake can be converted to ethanol via fermentation. Grain, usually used for consumer ethanol ^ 201204695 This ethanol is used as a fuel or consumer. In addition, fermentation of starch or cellulosic feedstocks competes with food sources, thereby limiting the amount of ethanol that can be used in industrial production. The production of ethanol by reduction of a compound burning k and/or other carbonyl groups has been extensively studied, and various combinations of catalyst support and operating conditions are also mentioned in the literature. In the case of burning acid, such as acetic acid, it will form during reduction, or in the side reaction, ethanol and other compounds. These two impurities limit the production and recovery of ethanol from this reaction mixture. For example, in a hydrogenation reaction, an ester is produced together with ethanol and/or water to form an azeotrope (aze〇tr〇pe) which is 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. State Patent No. EP02060553 describes a process for the conversion of hydrocarbons to ethanol involving the conversion of hydrocarbons to acetic acid and hydrogenated acetic acid to form ethanol. The stream from the hydrogenation reactor is separated to obtain an ethanol stream and an acetic acid/ethyl acetate stream which is then recovered to the hydrogenation reactor. However, the process for recovering ethanol from crude oils such as acetic acid, and/or other carbonyl compounds is still in need of improvement. SUMMARY OF THE INVENTION In a first embodiment, the present invention is directed to a process for purifying a crude ethanol product comprising hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; separating at least a portion of the crude ethanol product into a lighter a fraction stream and an ethanol product stream; and separating at least a portion of the light ends stream in the distillation column to produce an overhead stream comprising acetaldehyde and a residual stream comprising ethyl acetate without substantially acetaldehyde And its derivatives. In a second embodiment, the present invention is directed to a purification process for a crude ethanol product comprising hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product; separating at least a portion of the crude ethanol product into a light library stream and An ethanol product stream; and separating at least a portion of the fractionation stream in the vaporization column to produce an overhead product comprising: acetic acid, and a residual stream comprising ethyl acetate, wherein the distillation column is at a pressure above atmospheric pressure Under the operation. 5 201204695 [Description of the Invention] ί 2Inventive's step-by-step recovery to hydrogenation of hydrogenated acetic acid in the presence of a catalyst. The present invention relates to the recovery and/or production of heterogeneous products from the touch. A method of purifying ethanol. This process involves the separation of the ethanol from the crude ethanol mixture I, in the reaction process, preferably recovery of acetic acid inlet = 纟 1, π or time to hydrogenation reaction 11. Return (four) B in the hydrogenation reaction conditions: reverse, '4 to make more ethanol. Embodiments of the invention may be beneficial for recovering and/or purifying ethanol under a production mold. In the continuous mode, the ethylene path is separated from the acetic acid-containing acetic acid stream from the crude ethanol product. This allows the main portion of the acetic acid s to be removed from the process to be dispensed without accumulation throughout the separation process. However, it was found that even if the ethyl chain had a lower point than acetic acid (10), the detectable amount would be separated from the vinegar. If it is not under the theory, it can form various derivatives, and it has a higher point than the "free". These ethylene derivatives may include, for example, condensed, hydrated, and semi-reduced. Some semi-aged and acetic acid hydrate derivatives are unstable compounds and, therefore, are not readily detectable and quickly balance with the free form and the form of their derivatives. In addition, these compounds have low stability. It can lead to the formation of co-mystery, which inhibits the separation of some components from the process stream. When the ethyl acetate vinegar is separated from the raw stream, the heterozygous Ethylamine can be separated from the ethyl ester. After the separation of the ethyl acetate, the ethylene derivative can be Decomposes to acetic acid. For most applications of acetic acid, the most desirable condition is (10) little or no, so additional processing is required to eliminate the addition. In addition, the ethyl acetate stream is removed from the system. The acetaldehyde derivative will reduce the overall ethanol production. The present invention is preferably practiced by operating the distillation column at a pressure higher than atmospheric pressure to inhibit or prevent the separation of the ethylene organism without being bound by theory. It is believed that operating the distillation column at a higher pressure will facilitate the conversion of the acetaldehyde derivative to acetaldehyde. In general, the distillation column can operate under the pressure of converting the acetaldehyde derivative into acetaldehyde. Preferably, the pressure of the phreatic column is from 120 kilopascals (kPa) to 5,000 kPa, for example, from 200 kPa to 4,500 kPa' or from 400 kPa to 3,000 kPa. 201204695 Figure 1 is A schematic diagram of a system 100 for the production and recovery of ethanol in a hydrogenation process. Hydrogen 101 and acetic acid 102 are fed to reactor 103 to produce a crude product 1〇4. The crude product 1〇4 is fed to the separation zone and 105 produces an ethanol product stream 106 and The light ends stream 1〇7, which comprises acetaldehyde and ethyl acetate. The light fraction stream 107 is fed to a distillation column 108, such as an acetaldehyde removal distillation column, to produce a distillate stream 109 comprising acetaldehyde, and a residue. The stream 11〇, which comprises ethyl acetate. The acetaldehyde in the distillate stream ι〇9 can be returned to the reactor 1〇3. When the conversion is incomplete, the separation zone 1〇5 can also be separated to remove unreacted acetic acid 111, and / or non-condensable gas 112. Separation zone 105 condenses acetaldehyde and ethyl acetate from the reactor and is sent to light ends stream 1 〇 7. Light stream stream 107 may comprise, for example, from 10 to 9 Torr. % by weight, such as from 25 to 9 % by weight or 50 to 90% by weight of ethyl acetate, and from i to 25% by weight, as from Μ% by weight or 1 to 8% by weight of acetaldehyde. The light fraction stream may further comprise ethanol and water, generally less than 30% by weight. Further 3 liters of distillation column 108 is preferably at the above pressure '12 〇 kPa to 5 The operation of the distillate stream 109 is preferably from 6 Torr. (: to ii 〇 °c, for example, from 7 〇 ° c to 1 〇〇. (: or 75 〇 c to 95 ° C. The temperature of the residual stream 110 is preferably from 7 〇 c > c to 115. 〇, for example, 8 〇 匸 〇〇 〇〇 c or 85 ° C to ll 〇〇 c. The acetaldehyde is mainly removed from the distillation column 108 It is stored in the distillate stream 1〇9. The degree of the ethylene in the distillate stream may vary. So, as long as most of the acetic acid of the steamed scale (10) is removed, it can be stored in the 1G9. . Residue stream UG, phase =; this contains a small amount of (10) and (d) derivatives. In an embodiment, the concentration of the residual stream comprising the (10) derivative of the ethyl chain derivative is less than 1 «%, for example, less than 〇5 wt%, or less than the concentration of G_1 in the residual stream UG. If it may be less than 3% by weight 'for example, less than 2% by weight, or less than 丨% by weight _ good to be 'in the residual stream 110, the amount of ethylene and/or shrinkage is lower than the detectable amount. In the process of the invention, a stream containing almost all of the acetic acid is advantageously formed, and the

Increase ethanol production. During the process, it is also provided with acetic acid, which contains a low amount of acetaldehyde or no acetaldehyde, so that the purge stream is also suitable for other purposes. L ’, G 201204695 (4) can be used for any ethanol production using hydrogenation of acetic acid. Materials, catalysts, reaction conditions and further departures are further described below. The secret recipe (4) raw materials, acetic acid and hydrogen, can come from any source of puncturing, including natural pores, petroleum, coal, and biological materials. For example, acetic acid can be produced by methanol radicalization, ethylene oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. A process for the preparation of methanol for the production of acetic acid is described in U.S. Patent Nos. 7,208,624, 7,115,772, 7〇〇5 541, 6,657,078 ^ 6,627,770 ^ 6,143,930 . 5,599,976 ^ 5,144,068 ^ 5,026, ^ 908 ^ 5,001,259 and 4,994,608 'all of which are disclosed in This is included in the reference. Alternatively, ethanol production can be integrated with these sterol carbonylation processes. As oil and vocations fluctuate, (iv) the production of acetic acid and carbon, such as sterols and carbon monoxide, from carbon sources has attracted increasing interest. In particular, it may be advantageous to produce acetic acid from a syngas produced by any suitable carbon source when the price of oil is higher than that of natural gas. For example, U.S. Patent No. 6,232,352 discloses a method of modifying a methanol plant to produce acetic acid, which is hereby incorporated by reference. By modifying the methanol plant, it can significantly reduce or largely eliminate the large capital cost required to produce carbon oxides from new acetic acid plants. All or part of the synthesis gas is recycled from the sterol synthesis cycle, and a fraction of the recovered carbon oxide is provided, which is miscellaneous in the production of acetic acid. In a similar manner, the hydrogen used in the step can be provided by syngas. In some embodiments, some or all of the starting materials in the vinegar hydrogenation process described above may be derived in part or in whole from the syngas. For example, acetic acid can be formed from decyl alcohol and carbon monoxide, all of which can be used to syngas. It can be (10) φ partial oxidation reforming or steam heavy wire shaft, and - carbon can be obtained from the composite silk. At the same time, the nitrogen gas of the Yuxuan-shaped red axis product can be separated from the synthesis gas. Accordingly, syngas can also come from different carbon sources. The carbon source, for example, may be selected from the group consisting of natural gas, crude oil, petroleum, coal, biomass, and combinations thereof. Syngas or hydrogen can also be derived from biologically derived decane gas, which can be produced from landfills or agricultural waste. Where, in another embodiment, the acetic acid used in the hydrogenation step may be formed from fermentation of the biomass. In the fermentation process, it is preferred to produce a vinegar-producing process or to ferment sugars with the same (four) microbes to produce the acid, and, if any, a small amount of carbon dioxide as a by-product. The carbon efficiency of the fermentation process is preferably above 70%, above 80% or above 9%, whereas conventional yeast processes typically have a carbon efficiency of about 67%. Alternatively, the microorganism used in the fermentation process is Genus selected from the group consisting of Clostridium, Lactobacillus, Moorella, and thermophilic anaerobic bacteria Propionibacterium. a group of Clostridium propionicum, Gram-negative anaerobic bacteria, and Mycelia, and in particular, selected from the group consisting of Clostridium malic acid, Clostridium butyricum, Clostridium thermophilum (Moorella th_oacetica), odd A group of Thermoanaero-bacter kivui, Debruchi lactic acid bacteria, propionic acid bacteria, propionic acid helix g, Susinick anaerobic bacteria, Lactobacillus bacillus, and bacillus bacillus. In this process, all or part of the unfermented residue from the biomass, such as lignans, may be selectively gasified to form hydrogen, which may be used in the hydrogenation step of the present invention. A typical fermentation process for the formation of acetic acid is disclosed in U.S. Patent Nos. 6, Suction (10), W4, 6〇3, 7, 5G7, 562, 7, 351, 559, 7 Zheng, 865 and 7,888, 082 ′, all of which are incorporated herein by reference. See also U.S. Patent Application Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are incorporated herein by reference. Biomaterials include, but are not limited to, agricultural waste, forest products, grasses and other cellulosic materials L wood harvest residues, softwood chips, hardwood chips, branches, stumps, leaves, bark, sawdust, unqualified pulp, corn , corn straw, wheat straw, straw, sugar cane residues, = twigs, miscanthus, animal manure 'urban garbage, urban domestic sewage, commercial waste, grape talent, almond shell, walnut shell, coconut shell, coffee residue, grass Granules, grass balls 'wood balls, cardboard three sheets of paper, plastics and fabrics. See, for example, U.S. Patent No. 7,884,253, the entire entire of which is incorporated herein by reference. In addition, the source of the biological material is black liquor, a dark color It is a by-product of the conversion of wood into Kraft prceess, which can be dried to form paper. Black liquor is an aqueous solution of lignin residues, hemicellulose and inorganic chemicals. Patent No. 7, also incorporated herein by reference, which provides a process for the production of methanol by conversion of carbon materials such as petroleum, coal, natural gas and biomass. Hydrogenation and gasification of solid and/or liquid carbon materials to obtain process gas, "forming gas by pyrolysis of additional natural gas." The syngas is converted to methanol, and 201204695 = methanol, 歪 & The process also produces hydrogen, which is described in the above-mentioned U.S. Patent No. mm!, which discloses the process of converting waste biomass into a synthesis by gasification, and U.S. Patent No. 5,754 discloses hydrogen. Gas compositions, such as those comprising hydrogen and carbon monoxide, are described herein in their entirety. The acetic acid feed fed to the hydrogenation reactor may also include other carboxylic acids and anhydrides, as well as acetaldehyde and propane. Preferably, a suitable acetic acid feed stream comprises a group of one or more compounds selected from the group consisting of vinegar@0 anhydride, acetaldehyde ethyl acetate, and mixtures thereof. These other compounds can also be hydrogenated in the process rolls of the present invention. In some embodiments, the presence of a ship, such as propionic acid or its anhydride, may be advantageous for the production of propanol. Water can also be present in the acetic acid feed. In addition, acetic acid in the form of a vapor from a lysing unit can also be taken directly as a crude product, as described in, for example, U.S. Patent No. 6,657, issued toK. The ethanol synthesis reaction zone of the present invention does not require condensation of acetic acid and light ends or removal of water, thereby saving overall processing costs. The acetic acid can be fed in at the reaction temperature, and the hydrogen can be diluted with the hydrogen in the absence of hydrogen, or the hydrogen can be fed back relative to the carrier gas, for example, nitrogen, helium, carbon dioxide, and the like. In order to operate the reaction in the gas phase, the temperature in the system should be controlled so that the temperature is not lower than the dew point of acetic acid (DewpGint in the implementation of the towel, acetic acid can be 2 points of acetic acid under a certain pressure, New Zealand (four) acid can enter - The step is heated to the inlet temperature of the reactor. In another embodiment, the acetic acid is transferred to a state by a hydrogen gas, a recycle gas, another suitable gas or a mixture thereof at a temperature of the Sf_ point, so that the acetic acid vapor can be Humidifymg the carrier gas, and then heat the mixed gas to the reactor inlet temperature. Preferably, after the temperature is equal to or lower than 125t, the hydrogen and/or the recovered gas is passed through the acetic acid to transfer the acetic acid to the vapor state. The combined gas stream is reheated to the reactor inlet temperature. Some embodiments of hydrogenation of acetic acid to form an ethanol process may also employ a variety of configurations, including fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, "Adiabatic" reaction S can be used. In these embodiments using the "adiabatic" reaction ||, there is little or no need for anti-ship Human (10) pipe addition or removal. In other embodiments 201204695, radial flow reactors or reactor groups may be used, or a series of reactors may be used with or without heat exchange, quenching or introduction. Further feed. In addition, a shell-and-tube reactor with a heat transfer medium can be used. In many cases, the reaction zone can be placed in a vessel, or a series of vessels in which the heat exchanger is interposed. In an embodiment, the catalyst is used in a fixed bed reactor, such as a reactor in the form of a pipe or tube, wherein the reactants are typically passed in the form of a vapor or passed through a catalyst. Other reactors, such as fluidized beds, may also be employed. Reactor or Bumper Reactor In some cases, the hydrogenation catalyst may 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 with the catalyst particles. The reaction is carried out in the liquid phase or in the gas phase. Preferably, the gas phase reaction is carried out under the following conditions: The reaction temperature may be between 125. (: to 35 (TC, for example, from 200. (: to 325 ° C, from 2) 25t to 300. (: left or right 'or from 25〇u 3〇 (rc. pressure range from 1〇 kPa (four)) to 3,000 kPa', for example, from 5G kPa to 2, engraved kPa, or from kPa to ^00 kPa. The "vapor hourly space velocity" (GHsv) fed to the reactor may be greater than 500/hour—for example, 'greater than!, _/hour, greater than 2, 5 hours, or even greater than & Figure/hour. In terms of range, 'GHSV can range from 50/hour to 50,0(8)/hour, for example, from Baohour to 3_)/hour' from 丨泽小时 to 1G, _hour, or (10) 6.500M, B# 〇 Overcoming the pressure at the selected hourly space velocity (GH is better than the pressure drop of the urging pressure, _ does not disable the higher pressure, but does not go to the space velocity, for example, 5,000 / hour or 6 5 〇〇 / small. Two considerable pressure drops. «Over-reaction rides may encounter two moles of reaction filaments per mole of acetic acid, so that the ratio of hydrogen to acetic acid in the feed stream may vary, from about 100%, for example, from 50:1 to 1 : 50, from 20: 丄 to j: 2, 忐 ".1 to;: Μ is the molar ratio of hydrogen to acetic acid greater than 2: i, for example: big two feet; 2 or =: 11 201204695 contact or residence time There will also be large differences depending on the amount of acetic acid, catalyst, reactor, temperature and pressure. Typical contact times range from less than i seconds to more than a few hours. If a catalyst system other than a fixed bed is used, at least for gas phase reactions, the preferred contact time is between at least about 0.1 and 100 seconds. For example, from 〇3 to 80 seconds or 〇4 to 3 seconds. Hydrogenation of acetic acid to form ethanol is preferably carried out in the presence of a hydrogenation catalyst. Suitable hydrogenation contacts include a metal catalyst comprising a first metal and any one or more of the second metals, a third metal or any other metal, optionally supported on the catalyst support. The first metal and the optional second metal and third metal are selected from the group consisting of elemental periodic table ffi, ΠΒ, ΙΠΒ, ΙγΒ, ,, VIB, VIIB, VIII transition metals, lanthanide metals, lanthanide metals Any metal from the group of Groups IIIA, IVA, VA, or VIA of the Periodic Table of the Elements. Preferred metal combinations for some typical catalyst compositions include platinum/tin, ship/bismuth, balance chain, handle/nail, ki/chain, ming/ji, drill/platinum, cobalt/chromium, cobalt/ruthenium, cobalt/tin , silver / palladium, copper / palladium, copper / zinc, nickel / Ji, gold / handle, 钌 / chain and 钌 / iron. A typical catalyst is further described in U.S. Patent Nos. 7,6,8,744 and 7,863,489, the disclosure of each of which is incorporated herein by reference. In another embodiment, the catalyst includes a fine/sulfur type catalyst as described in U.S. Patent Application Publication No. 5/6% 〇9, the entire contents of which are incorporated herein by reference: The catalyst comprises a first metal selected from the group consisting of copper, iron, beginning, recording, nailing, palladium, turning, titanium, zinc, chromium, chain-turning and crane. Preferably, it is the first metal, from H, recorded and nailed. More preferably, the first metal is selected from the beginning and the bottom. In the present invention-embodiment, when the first metal system, preferably the catalyst towel, for example, is less than 3 weights, the amount is less than 9% by weight, and the price is increased by the expensive price. The medium may optionally further comprise a second metal, which is a group of lanthanum, manganese, lanthanum, chain, gold, and recorded chains. The best complement. If present, the second metal is selected from the group consisting of copper, turn, tin, chromium 'iron, cobalt, vanadium, tungsten, palladium, platinum. More preferably, the second metal is selected from the group consisting of copper and the second metal is selected from the group consisting of tin and antimony. In the actual mode, if the catalyst includes two or more metals, for example:

And - metal, the first metal can be used in an amount of from 0.1 to Η) by weight, for example from (U 12 201204695 to 5% by weight, or from 〇·1 to 3% by weight. The second metal is preferably used from 〇丨To the weight %, for example from 0.1 to 10% by weight, or from 〇1 to 5% by weight. For a catalyst containing two or more gold layers, two or more metals may be mutually The alloy of the alloy may be a metal solution or a mixture including a non-alloy. The ratio of the metal or the preferred metal: 1.1:1 may be slightly different depending on the type of metal used in the catalyst. The order is that the molar ratio of the first metal to the second metal is preferably 1 〇: 丨 to: 10, for example, 4:1 to 1: 4, 2: 1 to 1 ·· 2, 1.5: 1 to η 丨.5, .1 : 1.1 The catalyst may also comprise a third metal, which may be selected from any of the first or second metals listed above as long as the third metal is unique to the first and second metals. In a preferred third metal, the third metal is selected from the group consisting of uranium, palladium, ruthenium, copper, zinc, tin, tin and antimony. Self-drilling, if present, the total weight of the third metal is ^% by weight, for example, 0.1 to 3% by weight, or 0.1 to 2% by weight. · / Promoting turbidity to turbidity In the application mode, the contact support body, the polar __ language, the gamma read body, the support body, the support material and the support modifier 'the modifier adjusts the acid support or the modification of the support material The reading body _ is the 7-frequency of the weight of the ship, for example, from 78 to 97 liters, or from 8 〇 weight% = 5 to heavy = re-election of the implementation towel, supporting the _ content of the handle total weight of 0 5% by weight to 15% by weight, or from 8 to %. The catalyst ΑΜ' Μ 整个 整个 整个 体 体 包覆 包覆 包覆 包覆 包覆 包覆 包覆 包覆 包覆 包覆 = = = = = = = = = = = = = = = = = = = = = = In the field of ^^ surgery, there is a general knowledge of the body material, so that the formation of (10) subsoil conditions τ ^ ^ body 2 includes, for example, a stable metal oxide-based selective body biting pottery is 糸purchase.. The preferred branch 1 includes a body, for example: dioxide = 201204695, / alumina, IIA bismuth, such as: calcium metasilicate, pyrogenic cerium oxide, high purity cerium oxide and mixtures thereof . Other supports include, but are not limited to, iron oxide, aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbon, and mixtures thereof. As noted above, the catalyst support may be modified by the support modifier. In certain embodiments, the support modifier may be an acidic modifier that increases the acidity of the catalyst. Suitable for the support support modifier may be selected from the group consisting of Group IVB metal oxides 'Vb group metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VmB metal oxide oxides, and mixtures thereof. . The acidic support modifiers include those selected from the group consisting of titanium dioxide (Τι〇2), cerium oxide (Zr02), cerium oxide (Nb205), oxidation knob (Ta2〇5), aluminum oxide (ai2o3), and boron oxide (b2〇3). ), a group of phosphorus pentoxide (p2〇5), and antimony trioxide (Sb2〇3). Preferred acidic support modifiers include those selected from the group consisting of titanium dioxide (Ti〇2), oxidation cone (Zr02), niobium oxide (Nb2〇5), oxidation knob (Ta2〇5), and aluminum oxide (Αία). The acid modifier may further include tungsten oxide (w〇3), molybdenum oxide (Mo03), ferric oxide (Fe2〇3), chromium oxide (Cr2〇3), vanadium oxide (v2o5), manganese dioxide. (Mn〇2), copper oxide (Cu〇), cobalt oxide (c〇xian) or cerium oxide (Bi203). In another embodiment, the support modifier can be a basic modifier having low or no volatility. Such a basic modifier, for example, may be selected from the group consisting of: (bismuth alkaline earth metal oxide, (ii) alkali metal oxide, (iii) alkaline earth metal metasilicate, (iv) alkali metal metasilicate , (v) periodic table of lanthanum metal oxides, (vi) periodic table of lanthanum metal bismuth salts, (vii) periodic table 1 lanthanide metal oxides, periodic table [Liao  β group metal partial salt, and Groups of mixtures. In addition to oxides and meta-acid salts, other types of modifiers including nitrates, nitrites, acetates and lactates may also be used. An oxide of potassium, magnesium, calcium, strontium, barium, and zinc and a bismuth citrate, and a combination of any of the foregoing. Preferably, the support modifier is calcium citrate, and more preferably calcium bismuth citrate. (CaS [〇3]. If the support modifier comprises calcium metasilicate, it is preferred that at least a portion of the calcium metasilicate is in crystalline form. 14 201204695 The preferred dioxide stone material is SS6] 138 high surface (HSA) carrier (Saint-Gobain NorPro). This SS61138 dioxide dioxide contains approximately % by weight High surface area dioxane; surface area of about 25G flat material / gram; 咕 type pore analyzer = has a median pore size of about 12 nm, an average pore volume of about α cubic centimeters / gram; and the reactor bulk density of about 0.352 grams / Cubic centimeter (22 lbs/cub). The preferred oxidized stone eve/oxidized inlaid building material is KA-160 dioxide (Sud Che Xiang Company), with a nominal diameter of about 5 mm and a density of about Ο· %2 g / ml, the absorption is about gram of water / gram of support, the surface area is about 16 〇 to 175 square meters / gram, and the pore volume = 〇 68 liter / gram. The catalyst suitable for use of the present invention is preferably modified The sexual support is impregnated with metal, but he can also be used, for example, chemical vapor deposition. This kind of impregnation technique is described in the United States, 7_^4 t 参6ί4 heart and beautiful coffee 1 (four) public case number 2 197485, In this case, in particular, the hydrogenation of acetic acid can achieve a good conversion rate and the ratio of good if9". The conversion (4) accounts for the percentage of the supplement. The conversion rate is 3 = above 'for example, at least 20% At least 40%, at least ^ at least 10,000, or at least 80%. Although the catalyst has a high turn scale There are 0 products, for example, at least or at least 9G%, but in - there: ethanol, rate then 'lower conversion rate is also acceptable: this. 'In many cases through the #_ circulation or It is more difficult to make up the large reactor, but it is more difficult to make up for the low selectivity. The "selection rate" of the modified detection is based on the conversion of the acetic acid to the percentage change of the compound with independent selectivity, and the selectivity Also t turn 忒 two - = acetic acid 转化 acid conversion to ethanol, we refer to the choice of ethanol alcohol, ethylene and ethyl acetate. Preferred $ ethoxy compound ", specifically refers to the choice of B (four) The rate is above 8G%, for example, at least 201204695 has 85% or at least 88%. In embodiments of the invention, it is also preferred that there is a lower selectivity for the desired product, such as simmering, sulphur, and carbon dioxide. The selectivity of the product to be expected is lower than that of, for example, less than 2% or less than that which is not observed in the hydrogenation process. In some embodiments of the present invention, the rate of formation of hydrocarbons is low, desirably less than 2%, less than 1%, or at 0.5% of acetic acid converted to alkanes by a catalyst' and alkanes are used as There is not much value outside the burning. "Yield" refers to the specific activity of each Shike in the hydrogenation process, for example, the rate of 乙 per gram of catalyst per hour is _ gram of ethanol, for example, at least 2 hours per gram of touch 4 gram of ethanol or preferably at least gram of ethanol. In the present context, the yield is preferably from per gram of lake per hour to 3 · red alcohol, for example, 2,500 grams or 6 to 2, Operating under the conditions of the present invention, the level of ethanol production may be at least 每小时ι" 吨的醇', for example, at least budding ethanol per hour, at least 5 ticks per hour, or Every small two-scale ship produces ethanol, which depends on its regulation. The domain is at least 2.5 times per hour for the mother hour, for example: at least 15 oz ethanol per hour or: two if, ton of ethanol. In the case of large-scale industrial production of ethanol, ethanol can be produced from 0. 1 to 160 side hours, for example, from 15 to economic hours per hour from 0 to 80 4 ethanol. If ethanol is produced by fermentation, Light = not suitable for the implementation of the present invention, the method of the invention of different implementations The crude ethanol product obtained by the hydrogenation process, before any purification and separation, includes unreacted ethanol and water. The term "ethanol crude product" as used herein refers to bribes ^ a quantity of alcohol, and 5 parts by weight of water in a region of 35 wt%. In some examples, the crude ethanol product includes ethanol, which is 5% by weight of the total weight of the crude ethanol product, for example, '1 〇 weight hemp 6〇% by weight, or from 15% by weight to the total weight of the crude ethanol product. Preferably, the crude ethanol product 16 201204695 contains at least κ) by weight of ethanol, at least 15% by weight of ethanol or at least 2g. The weight of the alcohol. The crude ethanol product will usually include unreacted Wei, depending on the conversion rate, and the amount of the pot is, for example, less than 90 «% ', for example, less than (10)% by weight or less than % by weight. The 'unreacted acetic acid content is from 〇 to 9〇% by weight, for example, from 5 to 8 〇 from 15 to 70% by weight, from 20 to 7% by weight or from 25 to 65% by weight. Since water is in the reaction process Formed, the crude ethanol product will generally include water, for example, it contains From 5 weight = % to 35% by weight 'for example' from 1% by weight to 3% by weight, or 1% by weight to % = % by weight. In the process of hydrogenation of vinegar, or by side reaction, it will also be produced. Ethyl acetate, the content of which, for example, 'from 0 to 20% by weight', is from 0 to 15% by weight, from 1 to 12% by weight, or from 3 to 10% by weight. Furthermore, acetaldehyde can be produced by side reactions. The content, for example, from 〇 to 1〇% by weight, like from 〇 to 3% by weight, from 0.1 to 3% by weight, or 〇.2 to 2% by weight, other components 'eg esters, ethers, Aldehydes, ketones, alkanes, and dioxides may be less than 10% by weight 'if, for example, less than 6% by weight' or less than 4% by weight. In terms of ranges, the total content of these other ingredients may be reset from 〇1 to 1〇, for example, from 〇.1 to ό% by weight, or from 0_1裘4% by weight. The crude ethanol product is typically given in Table 1. 17 201204695 Table 1: Concentration of ethanol crude component (% by weight) Concentration (% by weight) Concentration (% by weight) Concentration (% by weight) Ethanol 5 to 70 10 to 60 15 to 50 25 to 50 Acetic acid 0 to 90 5 3. 80 15 to 70 20 to 70 water 5 to 35 5 to 30 10 to 30 10 to 26 ethyl acetate 0 to 20 0 to 15 1 to 12 3 to 10 jun 0 to 10 0 to 3 〇 _] to 3 0.2 to 2 Other 0.1 to 10 0.1 to 6 0.1 to 4 The crude ethanol product can be treated as shown in the typical hydrogenation system 200 of Figure 2. Figure 2 shows a hydrogenation system suitable for the separation of ethanol from a mixture of acetic acid and crude ethanol according to one embodiment of the invention. System 200 includes a reaction zone 201 and a distillation zone 202. Reaction zone 201 includes reactor 2〇3, hydrogen feed line 204, and acetic acid feed line 205. The distillation zone 202 includes a flash column 2〇6, a first distillation column 207, a second distillation column 208, a third distillation column 209, and a fourth distillation column 223. Hydrogen and acetic acid are supplied to the evaporator 210 through the hydrogen feed line 2〇4 and the acetic acid feed line 2〇5, respectively, and a gas feed stream is established in the line 2]1 to be directed to the reactor 2〇3. In one embodiment, the hydrogen feed line 204 and the acetic acid feed line 205 can be combined, for example, in a stream containing both hydrogen and acetic acid, fed together into the evaporator 21A. The temperature of the vapor feed stream in line 211 is preferably from 100 〇c to 350 〇c, for example, from 12 〇 〇 c to 3 〇. Mouth ^ 150 °C to 300%. Any unvaporized feed is removed from the evaporator 21, as shown in Figure 2 and can be recovered or discarded. Further, although Fig. 2 shows the top of the pipe-directed reactor 2〇3, the pipe 211 can be guided to the side of the 2〇3: The modification of the zone 2〇1 and the additional components are as follows. The square bottom reaction reactor 2〇3 contains a catalyst for hydrogenating a carboxylic acid, preferably acetic acid. In the embodiment or multiple guard beds (not shown) can be used to protect the poisons contained in the oil 0 or not expected. Such a protective bed uses a reduced or liquid flow. Suitable bed material materials have been disclosed in the literature and include, for example, carbon dioxide dioxide, oxidized sulphur, or a resin or resin. In some embodiments, 匕 protection 18 201204695 ==^ specific _, such as sulfur _ 素. In the case of hydrogenation, it is preferred to continuously react the money 3 to remove the crude ethanol product via line 212. The crude product stream can be condensed and sent to the flash tower, which in turn provides & gas and liquid (4) for avoidance to 25Qt, repair 22 = Ϊ " flash tower 2〇6 _ force is better from 50 thousand Pa to 2, _ thousand square ten, two: 5 kPa to 1,500 kPa or from 100 to i, 〇〇〇 kPa. In another implementation, the temperature and the force of the 2G6 are similar to the temperature and force of the reactor 2G3. The vapor stream of the second gas may include gas and carbon gas compounds which may be purged and/or passed through 2M'; The vapor of the return portion as shown in Fig. 2 passes through the compressor 214 and is combined with the helium oxygen feed to be fed into the evaporator 21A. The liquid is withdrawn from flash column 2G6 and pumped as a feed composition via line 215 to the side of first steam 207. The steam tower is also referred to as a staged separation tower. The content of line 215 will generally be approximately the same as that obtained directly from the reaction enthalpy, and JL may actually be determined as the crude ethanol product. However, it is preferred that the feed composition of the pipeline does not contain hydrogen, carbon dioxide, methyl and sulfur, which are removed by the flash column 206. The liquid turnover of the line 215 is shown in Table 2. It should be understood that the liquid line may contain ingredients that are not listed, such as ingredients in the feed. Eight 201204695 Ethanol Acetic Acid Water ~~~~ Table 2: Concentration (% by weight) 5 to 70 _ <90 5 to 35 Feed composition concentration (% by weight) ]0 to 60~~~ 5 to 80 5 to 30 concentration ( Weight %) 15 to 50 15 to 70 Acetate acetaldehyde ~ acetal awake · _ < 20 0 to 15 10 to 30 1 to 12 _ < 10 < 5 0.001 to 3 0.001 to 2 0.1 to 3 —八八----- Acetone other esters ' 0.005 to 1 -_15_ 0.0005 to 0.05 < 0.005 < 〇005 0_001 to 0_03 —----~ — Other ethers <5 < 0.001 Statins ——— __ <5 < 0.005 < 0.001 < 0.001 The amount shown in the table below (<) is preferably absent, and if present, there may be an amount ' or a weight greater than 0.0001%. i 2 two other si classes, which may include, but are not limited to, ethyl acetate, _", isopropyl acetate, and acetic acid. In Table 2, "other oxime, may include but scoop, methyl ethyl isobutyl b. or a mixture thereof. "Other alcohols" in Table 2 may be, but not limited to, methanol, isopropanol, n-propanol, positive Butanol or a mixture thereof. In an embodiment composition, for example, line 215, may include propanol, such as isopropanol and/or n- 〇 to % by weight, from the side to °. G 5% by weight. It should be understood from the toilet that these other ingredients can be incorporated into any of the distillate str's described herein and that these other ingredients will not be described further herein unless the crude product is passed through one or more separators. Separating hydrogen and/or others, the product can be fed directly into the acid: ", the vapor feed, rather than the non-condensable gases, can be recovered from the overhead of the distillation column. 20 201204695 Tian Lulu ^15, when the acetic acid content is less than 5% by weight, the acid separation steam tower 207 can be jumped "i- thing and the road 215 can be directly introduced into the second steaming tower 208, the second steaming hall The tower is also collectively referred to as 'fe proud steamed scales'. (d) In the embodiment shown in Fig. 2, the line 215 is the lower portion of the first steaming step 2, 7 and the lower half or lower half of J. According to the acetic acid conversion rate and the first steaming tower 207 = quite 'unreacted acetic acid, part of the water and other heavy arrogance, if any, will be removed from the composition of S Road 2丨5, better For continuous removal as a residue. In certain embodiments: where, in particular, having a higher acetic acid conversion rate, at least _, or at least 90% of the field: it may be advantageous to remove most of the water in the line 215, and in the residual stream 216 The middle side is all acetic acid. The residual stream 2丨6 can be recycled to the reaction zone 2 In addition, the water in the 2!6 t portion of the residual stream can be returned to the acid-rich portion of the reaction zone 2〇1 for separation and removal. In other embodiments, the residual stream 216 can be a dilute acid stream that can be treated with a weak acid, systemed, or sent to a reactive distillation column to convert the acid to an ester. An overhead is also formed in the first hot distillate column 207, which is removed in line 217 and can be condensed and refluxed 'e.g., at a reflux ratio from 1 G u to 丨: 1 G, as from 3: 丨 to 丨:3 or from 1: 2 to 2: 1. The steaming material of Figure 2 is any steaming tower that can complete the separation and/or purification. The steamer is a tray-type steamed scale having an i(9) tray, for example, and having 10 to 100 trays, 20 to 95 trays, or 30 to 75 trays. The tray can be a sieve tray, a solid (four) tray, a shift or any other suitable design known in the literature. In other embodiments, the tower can be steamed. In the case of a packed tower, both the structured packing and the scattered packing can be arranged such that the trays or packing can be arranged in a continuous inspection tower or in two or more steaming, so that the steam enters from the first stage. The second seat, and the liquid enters the first seat from the second seat and so on. With the associated condensation in each steamed!! and the liquid separation tank can be any conventional design and simplified for shooting. Heat can be supplied to the bottom of each fine tower at the bottom of the flow loop through the heat exchanger, or reboiler (ReboileO. Other types of re-follers can also be used, such as internal re-followers. Provide reboil (four) heat can come from any process The heat generated by the integration of the re-integration of the Buddha 201204695 other? Heating, or steel furnace. Although the use of additional reactor ',, condensation' = in: fJ invention method can be used in the field and ancient, S ~7 conge, heating 70 pieces and other components. For the technical compressor, then::====: each =, pump, and used in the process of the present invention. Know the "clutch (four)' may also be merged may be In terms of practical problems, although it can be used in one session with Γ耽 pressure and super atmospheric pressure, in these areas, the mountain shape is 10 kPa to 3,000 kPa. The temperature is generally between the field of transfer and the point of removal of the residue composition. For the blue technique; ==; _ pressure. In addition, depending on the scale of the production process. b彳不彳' If described , can be steamed in a standard atmospheric pressure with a feed weight ratio 2 〇 7 hours, from the steam tower to drain the pipeline 2 95〇c ^ 12〇〇c, ^ 105〇c ^ U7〇c ^ age 207 through the pipeline 2] 7 discharge _ discharge temperature needle: c, for example , from 75〇c to 95〇c or 80. to 9〇〇c. Yarn = heart to the first - steamed crane tower 207 pressure range from αι kPa to (10) kPa, for example, from kilopascals or from 1 kPa Up to 375 kPa. The composition of the residue in the exemplary embodiment is listed in Table 3 below. Please note that depending on the acetic acid, correcting the operation and whether most of the water is removed from the residue, these rates and steaming should be understood. Yes, "The substance and residue may also be ^ = changeable. The ingredients in the feed. In addition, for convenience, the first ingredient, like the skin, is called "first take," or "first residue" Other steaming == objects can also have similar digital repairs (second, third, etc.) to distinguish between subtle or residual terms should not be converted to require any specific separation order. 201204695 Table 3: ¥^^--- Concentration (% by weight) 7 exhibition original (fortunate concentration (weight distillate - - 里里 / 〇 J ethanol 20 to 75 ~ ^ 〇 Jl70 40 to 65 water 10 To 40 15 2? 20 to 35 acetic acid <2 〇.U〇1 φ 〇s 〇〇1 to 0.2 ethyl acetate <60 ——40 10 to 30 acetaldehyde <10 - to 5 0.01 to 4 <0.1 _ _ <〇.l ~ <0.05 Acetone <0.05 - 0.03 〇〇1 to 0.025 Residue ______ Acetic acid 60 to 100 — ~---_ —_Z〇J.95 85 $ Q9 Water &lt ;30 1 $ on 1 to 15 Ethanol <1 - Wang Yi <0.9 < 〇07 Secret Tower 207 - Some species, such as _, can be decomposed to very low levels and not further, in the discharge reactor After 2〇3, the pipeline liquid feeds the crude ethanol product. There may be hybridization. According to the vinegar concentration, the acid: cool. By means of the stop_ and/or temperature of the liquid feed 215, the distillate of the double column 207, such as the overhead stream, can be adjusted, preferably, the reflux ratio thereof is 5 In.]q ... claws such as the brother 2, the alcohol, the acid, the west, the pipeline 217, preferably include the water and other W, which is formed by the binary and ternary, half section. The first is slightly introduced to the top or middle portion of the first Lok Tower 208. For example, in the above mode, 208 is a tray type steaming or filling steaming. In - implementation or from 2〇 to ^1ζ2ί) 8=5 to 7_盘 '(four)' from 15 to 5〇 tray tray steamed sister, stomach = °9 _ 'If not water extraction 25 tray It. Then the official road 2Π can be introduced into the tray. In addition, if a tray tray distillation tower of 30 trays is used which does not utilize water extraction 23 201204695, in the pipeline type, the second steaming column 2〇8 may be the extraction 7 and may be introduced into the tray 2. In another implementation, such as water, it can be added to the second steaming '8' °. In this embodiment, the extractant, the source or the (10) from the extract comprises water, and the shot may be from some external real-life formula, in the late _ _ mail H. _, can be used - piece or multi-piece =:,::= two _ under gas pressure operation, the first will be different, the second steaming view is better at the height from listening to 9 (). . ,;, the second residue temperature discharged by the official road 218 from the first - heart L from 耽 to 9 〇 ° c, or thief to the thief. .... The temperature of the second distillate discharged through the official road 220 is preferably from 5 Torr to 90 ° C, for example, from 60. "5 snv , . Pingyi 1 main has two to pressure, that is, i Ji or to 7G C ° second steaming can be operated under low vacuum conditions, which is beneficial to further separate acetic acid And B. leaven. In its practice, the second steaming pressure range is from (U kPa to 510 kPa), for example, from j kPa to 475 kPa or 丄 kPa to 3 kPa. The composition of the second steamer 208 and the residue (four) are provided in Table 4. It should be understood that the exhibits and residues may also contain other ingredients not listed, such as other ingredients in the feed.

24 201204695 Concentration (% by weight, r^2__ Tad's weight%) Concentration (% by weight) Ethyl acetate acetaldehyde 10 to 90 1 £25 ~~~~~ to 90 50 to 90 Water 1 to 2 ~~~ to 15 1 to 8 Ethanol <1〇~ s_L to 20 4 to 16 Acetal to 15 0.01 to 5 to 2 0.01 to 1 Residue - 1 - ^ Water 5 to 70 _ Ethanol 20 to 9" ~~ s^ to 60 30 to 50 ethyl acetate "^3~~~ _____55 to 70 40 to 70 acetic acid ~~ <〇1 ~~~ to 2 0.001 to 0.5 U^l to 0.3 0.001 to 0.2 2- The weight of ethanol in the residue is preferably at least 3:], for example, at least 6:, at least 8:1, at least (four) or at least ΐ5:ι. In the second residue B (b) second _ _ B 6 is better than the like: lower than 0.2:1 or lower than 0:1: as in the implementation of the second steaming tower In the method, the weight ratio of ethyl acetate to the ethyl acetate in the second residue in the second residue approaches zero. = the second residue is introduced into the third distillation M9: lower '; two; For example, at reflux ratio from i: 1〇 to 1〇: Bu, Jia is as shown in Figure 2 or from 1: 2 to 2:]. In the third step 3 to 3 of the line 221: the water is contained, preferably removed from the system 2〇〇 or partially returned to the money " preferably the main = steamer tower 2〇9 is preferably as described above Tower-type steaming tower, = what part. The first knowledge. From the third steaming 209 through the line 219 2 under atmospheric pressure 25 Le-er peak temperature is preferably 201204695

!:^rG°c to Saki or to the machine. _ Tower in the atmosphere to 115 ° C "The third residue temperature of the ' 攸 second Luo scale 209 is preferably from 70 ° C, from the thief to 110 ° C, or pit to Yang. C. Third Zena 209 The feed and residue may also contain other unlisted ingredients, such as ingredients in the feed. Distillate Ethanol Table 5: Distillation column concentration (% by weight) Concentration (% by weight)

Any compound that is passed through the steaming or subtraction of the condensed product in the third product is less than (U «%, for example, less than (10)% by weight or less than G 〇 2% by weight' The percentage is for the third "total weight". In an embodiment, a plurality of side streams can be removed from any distillation column 207, 2, 8 and/or 2, 9 in system 200. Preferably, at least the side stream is used to remove the impurities f from the third steaming tower 2〇9. These materials may be removed and/or retained within the system 200. The third distillate 219 may use one or more additional A separation system, for example, a distillation column (such as 'Jingde Tower'' or a sub-screen, is further purified to form an anhydrous ethanol product ""anhydrous ethanol finished product"." The second saturated material is preferably refluxed as shown in the second embodiment, for example, at a reflux ratio of 1:30 to 30:1, for example, from i: 5 201204695 5 · J 1*3 223,3 ·]. The second distillate is fed into the fourth distillation column through the pipeline 220. The fourth distillate is separated in the fourth steaming tower 223. The second German includes A: m: ” is included in the official road 224 Acetaldehyde, and the fourth residue, which is 20. ethyl acetate. The fourth museum is preferably from 1:20 to 15:1 or 1:10 in the reflux ratio from 1:20. Or 10] returning, and partially returning to the reaction zone 201 by the line 224. For example, the fourth splash may be attached to the evaporator 210, or directly added to the reactor. As shown, the theoretical two bundles, The four" and acetic acid - feeds the evaporator 210. If it is not added to the (four) denier hydrogenation to form ethanol ' (10) flow to the reaction zone, it can be (not shown in the reduction of by-products and waste generation) In another embodiment, in order to produce useful (10) collectable and _(10) 'purification with or without further steps, the derivative includes but is secreted to n-butanol, hydrazine, 3·1^ alcohol and/or croton road. And washing the fourth residue of the fourth steaming na. 223. The fourth residue is mainly packaged, which can be suitably used as a solvent mixture, or used in the production of Lai. In the fourth article of the fourth steaming 223, the material is removed, so that The residue in the fourth 4 distillation column 223 does not have a detectable amount of ethylene. The fourth steaming tower 223 is preferably operated as the tray two as described above. In one embodiment, the pressure is from 4 = 5 GG kPa, or from 4 GG kPa to 3, _ kPa. In the = fine formula, the fourth steaming tower 223 can be at a higher pressure than other steaming The fourth temperature of the steaming tower 223 discharged through the line 224 is preferably 60 C to 110 c, for example, from 7 〇〇c to 〇c or 75 〇c to the atmospheric pressure of the coffee. _ force operation, from the fourth distillation column 223 through the line 224 discharge temperature at least 赃, for example, at least 7 ^ 224f = fourth museum steam ota 223 discharged through the line 225 to leave === For example, from 8〇〇Cf7U〇〇C, or coffee to 峨. Residues discharged from the fourth tough tower 223 via line 225 when operating above the 201204695 == operation, "the preferred one is at least 7 Gt, for example, at least a thief or = residue 胍 傲 和 and residue The typical composition of the composition is listed in the next fourth tower and the residue may also contain other ingredients not listed,

Two = 9 = ... 96 峨 ethanol, for example, from 8 ° to _ alcohol, the hundred fresh line for the total sine. Typical ethanol finished product composition ranges are listed in Table 7 below. 28 201204695

The ethanol composition completed by the present invention preferably contains other alcohols other than s%, such as decyl alcohol, butanol, riuri, less than 〇5 by weight, an embodiment t, in the finished B (10) (four) Alcohols. In the alcohol 'for example, from 95 to (10) by weight, from (10) to the weight of p'〇〇0" from two to 500 ppm by weight. In one embodiment; the upper part 'optionally includes less than 8 weights and is formed. The substance is substantially free of the weight of PPm. Li Peng is less than 5 weight iPPm, or lower than! In some practical methods, 'when using further water separation, the ethanol product can be taken out as the water separation unit ^ logistics In this embodiment, the concentration of ethanol may be the same as listed in Table 7, and the car is better than π% by weight, such as greater than % by weight or greater than 99.5% by weight of ethanol. Preferably, the ethanol product comprises less than 3% by weight of water, such as less than 2% by weight or less than 5% by weight of water. The completed ethanol composition of embodiments of the present invention is suitable for use in a variety of applications including fuels, / Mixtures, chemical raw materials, pharmaceuticals, detergents, disinfectants, hydrogenated delivery or consumer products. In the fuel application 'denatured ethanol composition and can be mixed with gasoline for motor vehicles, such as cars, boats and small piston engine aircraft. In non-fuel applications , Denatured ethanol compositions can be used as solvents, detergents, disinfectants, coatings, inks and pharmaceuticals for cosmetic and cosmetic preparations. The ethanol composition of 2012-02695 can also be used as a process material, photochemical and latex processing.彳, 昝乐产-, food preparation, dyed finished ethanol composition can also be used as acetyl acetate, acetate acetate, ethylene, Λ ', his chemical materials, such as cool, also 曰In another case, the composition of the ethanol finished product can be drawn into any known dehydration catalyst to make (4) dehydration === stone catalyst, for example, can be used as dehydration catalyst, this: internal reference. 0.6 nm, the preferred Buddha stone includes a dehydration catalyst from a group of two pores having at least a stone X and a zeolite γ. 1 stone t is selected from the group consisting of mordenite, ·5, a boiling point, and a buddha Y description = 7^ Dedicated «_, 244 考. Judgment 3,130,007 broken, the entire contents of which are incorporated herein by reference. [Embodiment] An embodiment is provided below. The following embodiments are described in order to make the disclosure of the present invention more effective. Various distillation processes of the invention. EXAMPLES Example 1 includes ethanol, The crude ethanolic product of acetic acid, water and ethyl acetate was evaporated at a mean temperature of 2910 C and an outlet pressure of 2,063 kPa, in the presence of a catalyst, including 95 2% by weight of acetic acid and 46% by weight of water and hydrogen. In response to the reaction, the catalyst was supported by 16% by weight and 1% by weight of tin in 1/8 inch of strontium strontium sulfate-modified extrudate (Extrudates). Unreacted hydrogen was recovered. The reactor inlet is such that at a GHSV (gas hourly space velocity) of 3893 hr-1, the total hydrogen/acetic acid molar ratio is 58. Under these conditions, 42.8% of the acetic acid is converted and the selectivity to ethanol is selected. It is 871%, the selectivity to ethyl acetate is 8.4%, and the selectivity for age is 35%. Purification of the B-product by the separation of the flow of the 201204695 = tower shown in Figure 2 to produce the ethanol product stream and the arrogant f-iron Lai people 1 shot straight _ _ _ De Xiu test tower (0丨d (10) haw extinction (post)), its package 1 2 2 1 ' and the light library flow system is designed to operate under higher pressure to produce the top output catch '/, including the E disk, and the residual stream, which includes acetic acid 4, Under the pressure, the pressure difference between the trays in the test tower is 22 kPa back: = 8 is refluxed to the distillation column. At least some of the towers return to the logistics and return to (4) Remaining logistics == 8 speed to remove the wreckage. Light feed, tower paste composition Light fraction feed 14*%) Table 8 Acetaldehyde removal distillation tower Tower top store (% by weight) Residue (% by weight)

Example 2 S3 is: = the crude ethanol product of ethyl acetate is at an average temperature of ι〇·2^, and the selectivity is 87.9%, and the selectivity for acetic acid is 9.5 31 201204695 % 'B The wake-up rate is 1.8%. The crude ethanol product was purified from 筮9. Separation flow chart of 2 rows without thin towers Ϊ2: Retention: flow, which includes ethyl acetate. The distillation column was operated at a pressure of 274 kPa, and the pressure difference between the 塔 and == middle trays was i 2 kPa. The tower pastes out the stream and at least a portion of the overhead stream is returned to, and distilled. Logistics is removed. Light feed, tower top _ domain === 9 speed will remain

Feeding people! Inch diameter Aldshaw steaming, which consists of a tower tray, W-touch design, operating at a higher pressure to produce tower shed logistics, 1 package of red, example 3 = discussion - (four) difficult to turn The root produces ethanol crude product and is separated into a light saturated stream. The way of appreciating the month of the month is as follows: The table below shows that the amount of B in the feed of the proud flow is increased. For the purposes of this example, the two retention streams were from three experiments. The results are summarized in the table below and in Figure 3. . The same operating pressure

Experiment A The light fraction stream was fed to an acetaldehyde removal distillation column stream to produce a column top 201204695 column containing 25 trays and designed to operate at a higher pressure of 220 kPa. The top of the tower is proud of the return of the material. The ratio (D/F) of the feed in the tower is about G] (weight = = to, the tower has a temperature of 90-2i. The result of the separation experiment is 罝). _ Tower of the tower Table 10 - Acetic acid · Remove steam tower (at 220 kPa)

Ingredients Water Acetaldehyde Acetic acid Ethanol Ethyl acetate Condensed in acetone * Found in the case of residual flue, the experiment Β The light distillate stream is fed into the distillation column to produce a column top stream, which comprises ethyl acetate. The 移除 移除 乙 乙 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和 和The temperature of the tray _26 is 〇26. The results of the separation experiments are listed in Table 33 201204695 Table 11: Acetaldehyde shifting 13⁄43⁄43⁄4 (operating at atmospheric pressure) Column top Lt*%) Ingredients Light fraction feed (% by weight)

The acetal* is found in the residual stream to be about 4% by weight of the steaming tower. Experiment c The light fraction stream is fed to the acetaldehyde removal distillation column to produce an overhead product, which contains the overhead stream. It includes ethyl acetate. The acetaldehyde removal distillation column is a 2-inch acetic acid' and a residual column, which contains 60 trays and is designed to operate at subatmospheric pressure. , Deschau distillation pressure operation. The top of the column was refluxed to a steaming grid at a reflux ratio of about 〇75, and the ratio of the feed to the feed (D/F) was about 0.38 (w/w). . The temperature of the tray -26 of the remainder-distillation column was 53.2 °C. The results of the separation experiments are shown in Table 12 34 201204695 Ingredients Light distillate feed (% by weight) Table 12: E-ship i at 34kpa

* The % of B-fed to the steaming tower found in the residual stream is about 7.3%. The overhead crane (4*%) 4.69 2.95 操作 The operating pressure found in the residue compared to the light fraction feed. Drawing, as shown in Figure 3. According to Fig. 3, ==== dusting force, resulting in the percentage of the residual in the residual is lower than the cold light 腑 feed ^, age, although the invention has been purely detailed, but in the invention It is obvious that the limbs are familiar with this technique. The background and detailed description of the relevant knowledge and technical literature are discussed above, and the disclosures are hereby incorporated by reference. In addition, it should be recognized that the aspects of the present invention and the various embodiments and the following various features and/or the scope of the appended claims may be combined or interchanged in whole or in part, as described in the foregoing description of the various embodiments. Another embodiment can be combined with other real money, and the familiar artisan will understand. It is to be understood by those skilled in the art that the foregoing description is only illustrative and not intended to limit the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in detail below with reference to the various drawings, wherein like numerals refer to the same elements. Figure 1 shows a flow chart of a hydrogenation system in accordance with an embodiment of the present invention. Fig. 2 is a flow chart showing a gasification system according to an embodiment of the present invention. Figure 3 shows the operating pressure of the removal of the distillation column to remove the acetaldehyde; the main component is explained. Code Description 100 System 101 Hydrogen 102 Acetic acid 103 Reactor 104 Crude product 105 1 —. Separation zone 106 Ethanol product stream 107 light fraction stream 108 distillation column 109 distillate stream ^~ 110 residual stream 111 unreacted acetic acid 112 non-condensable gas 200 hydrogenation system 36 201204695 code description 201 reaction zone 202 distillation zone 203 reactor 204 hydrogen feed Inlet line 205 Acetic acid feed line 206 Flash column 207 First distillation column 208 Second distillation column 209 Third distillation column 210 Evaporator 211 Line 212 Line 213 Line 214 Compressor 215 Line 216 Residual stream 217 Line 218 Line 219 Line 220 Line 37 201204695 Code Description 221 Line 223 Fourth Distillation Column 224 Line 225 Line 38

Claims (1)

201204695 VII. Patent Application Range: 1. A process for purifying crude ethanol product, comprising: hydrogenating acetic acid to form a crude ethanol product in the presence of a catalyst in a reactor; separating at least a portion of the crude ethanol product to produce a light fraction And a stream of ethanol product; and separating at least a portion of the light ends stream in the distillation column to produce an overhead stream comprising acetaldehyde and a residual stream comprising ethyl acetate, wherein the residue stream is substantially free of acetaldehyde And its derivatives. 2. The process of claim 1, wherein the acetic acid is formed from decyl alcohol and carbon monoxide, and each of the sterols, carbon monoxide and hydrogen used in the hydrogenation step is derived from syngas, wherein the syngas is derived from carbon The source is selected from the group consisting of natural gas, crude oil, petroleum, coal, biomass, and combinations thereof. 3. The process of claim 1, wherein the residual stream comprises from 1% by weight to 0.5% by weight of acetaldehyde. 4. The process of claim 1, wherein the residual stream comprises less than 9% by weight of acetaldehyde and derivatives thereof. 5. The process of claim 1, wherein the residual stream comprises less than 3% by weight of acetals and derivatives thereof. 6_ The process of claim 1, wherein the residual stream comprises from 4% by weight to 100% by weight of ethyl acetate. 7. The process of claim 1, wherein the residual stream comprises less than 4% by weight of ethanol. 8. The process of claim 1, wherein at least a portion of the tower is returned directly or indirectly to the reactor. 9. The process of claim 1, wherein the overhead stream comprises from 2% by weight to 80% by weight of acetaldehyde. 10. The process of claim 1, wherein the distillation column is operated at a pressure above atmospheric pressure. 39 The process described in 201204695, wherein the steaming tower is in the process of 12G kPa to 5, _, wherein the steaming is in the process of 4 (8) kPa to 3, _ 13. The process described in which the residue stream is discharged by a steaming tower. The process described in item 1 of the claim 1, wherein the steaming tower is operated at a pressure which facilitates conversion of the ethylene derivative to acetaldehyde. 16. The process of claim </ RTI> wherein the catalyst comprises a metal combination selected from the group consisting of platinum/tin, platinum/ruthenium, _, _, _n^n, ruthenium, cobalt/tin, silver /Palladium, copper/palladium, copper/zinc, nickel/palladium, gold/palladium, rhodium/chain and nail/iron group 0. 17. Process for purifying crude ethanol product, which comprises: catalyst in the reactor The acetic acid is hydrogenated to form a crude ethanol product; the knife is separated from the J-part ethanol crude product to produce a light saturated stream and an ethanol product stream; and at least a portion of the healthy stream is separated in the steaming tower to produce a top The museum produces, potted aldehydes, and residual streams, which include acetonitrile gambling, in which the steaming tower is held under high pressure. % main, wherein the distillation column is operated at 120 kPa to ‘where the arion is operated at 400 kPa to 18. The process described in claim 17 is 5,000 kPa. 19. Operate at a pressure of 3,000 kPa as described in Section 7 of the patent application. Wherein the overhead stream is withdrawn from the distillation column. 20. The process described in item 7 of the patent application, the temperature of the stream is from 60 ° C to 110. 〇 ' wherein the residual stream is discharged from the distillation column 21. The process temperature as described in claim 17 is from 70 ° C to 115 ° C. 201204695 22·For example, the method described in Item 17 of the scope of the patent application is directed to the reaction-oriented reaction. ‘Reducing at least part of the taring crane 23· 5% of the rib weight as stated in the mouth of the patent application. Wherein the ethyl chain stream comprises from 2% by weight to 24. ethyl acetate as described in claim 17 to 100% by weight. $里冲 25_ As described in the patent application scope item n, the Gan A#, Wei Shi and its derivatives. In the first step, wherein the residual stream is substantially free of the ethylene path, wherein the residue of the stream contains less than 1 weight. 26. The process described in the πth item of the patent application, and the derivative thereof. The process described in claim 17 wherein the stream residue comprises less than 3% by weight of acetals and derivatives thereof. The process described in claim n, wherein the steaming is operated at a temperature and pressure which facilitates conversion of the ethylene derivative to acetaldehyde. 29. A process for purifying a crude ethanol product, comprising: removing at least a portion of the crude ethanol product to produce a light fractional stream and an ethanol product stream; and separating at least a portion of the light library stream in the steaming tower to produce a column Dingde, which includes acetic acid' and a residual stream, which comprises ethyl acetate, wherein the residual stream is substantially free of the E-plate and its organism.