TW201127793A - Process for purifying a crude ethanol product - Google Patents

Abstract

Recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid. Separation and purification processes of the crude ethanol products are employed to allow recovery of ethanol and remove acetal impurities.

Description

201127793 five

117 Description Line 118 119 120 123 Line Line Line Line Line 4th Distillation Column Line 124

Ion exchange resin reactor bed

If there is a chemical formula in this case, please disclose the chemical formula which is the most incapable of showing the characteristics of the invention. VI. Description of the invention: The priority claim for the invention of the invention is based on the US patent provisional application filed on February 2 of the toilet year. U.S. Patent Application Serial No. 3, 332, 728, filed on May 7, 2010, and U.S. Patent Application Serial No. i. And the disclosure is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates broadly to a process for producing and/or purifying ethanol, and more particularly to a process for purifying a crude ethanol product obtained by hydrogenation of acetic acid. [Prior Art] The ethanol used in the industry is conventionally derived from petrochemical feedstocks such as petroleum, natural gas and coal, from feed intermediates such as syngas, or from starchy feedstock materials or cellulosic feedstock materials such as corn or Sugar cane, produced. Conventional production methods for petrochemical feedstocks and ethanol from cellulosic feedstocks include ethylene acid catalyzed hydration, methanol homologation, direct alcohol synthesis and "Fischer-Tropsch synthesis." The price of unstable petrochemical feedstock materials will cause fluctuations in the cost of ethanol produced in the traditional way. When the price of raw materials rises, the demand for ethanol from alternative sources is more demanding. The starch raw material and the cellulose raw material can be converted into ethanol via fermentation. However, fermentation is usually used for consumer ethanol production, which is used as a fuel or consumer. In addition, fermentation of starch or cellulosic feedstock competes with food sources while limiting the amount of ethanol that can be used in industrial production. The production of ethanol via reduction of alkanoic acid and/or other carbonyl compounds has been extensively studied, and various combinations of catalysts, supports and operating conditions are mentioned in the literature. The reduction of an alkanoic acid, such as acetic acid, with other compounds can form ethanol or form a reaction in the form of ethanol. For example, in the hydrogenation reaction and/or the subsequent side reactions, the ester is produced together with ethanol and/or water to form an azeotrope, which is difficult to separate. In addition, when the incomplete unreacted acid remains in the crude ethanol product, it must be removed to recover the ethanol. Accordingly, there remains a need for improved techniques for recovering ethanol from crude products which are reduced by an alkanoic acid such as acetic acid, and/or other carbonyl compounds. 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 a reactor in the presence of a catalyst to form ethanol comprising ethanol, water, ethyl acetate and acetic acid. a crude product in which the amount of the reduced amount is the first amount; and in the first steaming tower

S 4 201127793 in the second portion ^ residue (10) 'which includes acetic acid, wherein the first portion of the large alcohol = purification process: its, alcoholic hydrazine product, and in the first _ separation two: B: two museums' it includes Ethanol, water, ethyl acetate and shrinkage, and the first residue, which includes acetic acid, and hydrolyzed in at least part of the __ library. In one embodiment, the present invention is directed to a purification process for a crude ethanol product, the process comprising hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product comprising ethanol '= acid B from day, water, acetic acid and Reducing at least a portion of the crude ethanol product to form a hydrolyzate; and separating at least a portion of the hydrolyzate from the first column to a first-preparation, including ethanol, water, and acetic acid, and the first residue, It includes acetic acid. [Description of the Invention] The present invention relates to the recovery of ethanol from crude ethanol products. In particular, the present invention relates to a process for recovering and/or purifying ethanol from a crude ethanol product, preferably obtained by nitriding acetic acid gas in the presence of a catalyst. Process. Hydrogenation of acetic acid to form ethanol and water can be represented by the following reaction:

〇 CH

23⁄4

+ H20 Theoretically, when all of the acetic acid is converted to ethanol and water, the resulting crude product composition will include 72% by weight of ethanol and 28% by weight of water. However, if less than all of the acetic acid is converted to ethanol during the reaction process, additional compounds are formed. Acetaldehyde, for example, is an intermediate in the hydrogenation reaction process and may form acetals with hydrogenated alcohol products 201127793 (acetals). The desired ethanol product may react with acetaldehyde to form diethyl acetal (DEA ' Diethyl Acetal, also referred to as acetal). DEA and other acetals such as ethyl propyl acetal are impurities which are difficult to separate from the desired ethanol product. Therefore, acetals should be minimized or eliminated from crude ethanol. In addition, the formation of DEA consumes the desired ethanol, resulting in a decrease in the efficiency of ethanol production. In some embodiments, the feed stream introduced into the distillation zone 'eg, crude ethanol product' may contain acetals in an amount greater than 〇〇〇〇 5% by weight 'eg, greater than 0.01% by weight' or weight greater than (9), Percentage is the total weight of the total weight of the feed stream. In terms of ranges, the acetal content in the feed stream may range from 〇〇〇〇5 wt% to 5% wt%, for example, from 〇001 wt% to 3% wt% or 〇〇1 wt% to 1.5 wt%, This percentage is the total weight of the total weight of the feed stream. It has now been found that acetals, such as diethyl acetal, ethyl propyl acetal, ethyl butyl acetal and their hemiacetals, which are contained in crude ethanol, are preferably hydrolyzed in the distillation zone. It is especially preferred to hydrolyze in one or more distillation columns. Preferably, the acetal is hydrolyzed to form ethanol and acetaldehyde. The acetals in the crude ethanol product are preferably hydrolyzed in one or more distillation columns such that any stream removed from the distillation zone includes any stream that may be recovered to the reaction zone by the vapor zone, by weight, in comparison to ethanol The crude product contains less acetal. The content of acetal in the crude ethanol product is preferably from 1 〇〇: 1 to 2: 1, from 5 〇: 1 to 5: 1, or 25: 1 to 8 by weight of the acetal removed from the distillation zone. : 1. In a preferred embodiment, the ethanol recovered from the crude ethanol product is substantially free of acetals. For example, the acetal content in the recovered ethanol may be less than 〇 5% by weight, for example, less than 〇 1% by weight, or less than 0.005% by weight, based on the total weight of the recovered ethanol. In a typical embodiment, the acetal is hydrolyzed in the acid separation distillation column in the crude ethanol product, such that the two streams removed from the acid separation distillation column are fed to the distillation zone, ie, the crude ethanol product, by weight, Contains less acetal. The weight of the acetal content in the crude ethanol product is preferably from _:丨 to 2:1 ' from 50:丨 to 5:丨, or From 25: 丨 to 8 u. The acid separation distillation column overhead may comprise less than 5% by weight acetal, for example, less than 2% by weight or less than i by weight, based on the total weight of the collateral. The residue of the acid separation distillation column may contain less than 0.5% by weight, for example, less than 0.001% by weight or less than the o.oooi% by weight of the acetal, which is based on the total weight of the residue. Preferably, it is an acid separation distillation column residue

S 6 201127793 There is essentially no detectable acetal. The acetal weight content of the distillate and residue of the acid separation distillation column is preferably less than the acetal content introduced into the acid separation column feed. The amount of acetal in the feed is reduced by less than 50% in the distillate acetal content, for example: at least 75% or at least 90%. The amount of acid reduction in the feed is reduced by at least 50%, for example, at least 75%, or at least 90%, over the total content of the effluent and the residue acetal. In one embodiment, the acid catalyst can be used in an acid separation distillation column. If not bound by theory, it is believed that residual acid in the crude ethanol product can act as a catalyst for the hydrolysis reaction. Although hydrolysis may occur in one or more other steamed towers in the steaming zone, it is preferred that the chain is hydrolyzed in the acid separation column. For example, in one embodiment, Dea in the distillate of the acid separation vapor column can be hydrolyzed in a light fraction distillation column. In another embodiment, the &quot;ion exchange resin reactor bed can hydrolyze the DEA in the crude ethanol product, or any subsequent crude ethanol product in the reactor bed using the DEA in the intermediate distillation stream. The ion exchange resin can be an acidic or basic catalyst. Preferably, the ion exchange resin catalyst employed in the reactor bed comprises a solid acid catalyst or an acid ion exchange catalyst. The ion exchange resin reactor bed can be located outside of any distillation column or inside the distillation column. In one embodiment, the overhead of the acid separation distillation column is introduced into an ion exchange resin reactor bed to hydrolyze the DEA present. In another embodiment, the ion exchange resin can be located in one or more distillation columns, for example, in an acid-depleted de-tower and/or in a sub-distilled steam tower. The ethylene road and ethanol produced by the hydrolysis reaction can be returned to the reactor or further processed in one or more steaming towers. Embodiments of the present invention are useful for the recovery and/or purification of ethanol on an industrial scale. Suitable hydrogenation catalysts include a catalyst comprising a first metal and any one or more of the second metals, a third metal or other metal, optionally carried on the catalyst support. The first metal and the optional second metal and third metal are selected from the group consisting of 冚, ΠΒ, IIiB, IVB, VB, VIB, VIIB, or νπ 过渡 transition metal 'steel-based metals, group of dairy metals or Any metal selected from the group consisting of the Periodic Table of the Elements, IVA, VA, or VIA group. The preferred combination of metals in some typical catalyst compositions is selected from the group consisting of platinum/tin, platinum/rhodium, platinum/rhodium, palladium/palladium, palladium. / 铢, cobalt / palladium, cobalt / turn, cobalt / chromium, cobalt / bismuth, silver / Ji, copper / handle, nickel / handle, gold, 钌 / 铢 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. 7 201127793 In an exemplary embodiment, the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, nickel, nails, money 'hands, hungry 'silver, new, titanium, zinc, chromium, bismuth, turn, and Group of cranes. Preferably, the first metal is selected from the group consisting of an m chain and a hydrazine. More preferably, the first metal is selected from the group. When the first metal is platinum, it is preferred that the platinum content in the catalyst is less than 5% by weight, such as less than 3% by weight or less than 1% by weight, due to the expensive price of platinum. As noted above, the catalyst can optionally further comprise a second metal which will generally act as a promoter. If present, the second metal is preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, ruthenium, tungsten, palladium, platinum, rhodium, ruthenium, manganese, osmium, iridium, gold, and nickel. More preferably, the second metal is selected from the group consisting of copper, tin, cobalt, ruthenium and nickel. More preferably, the second gold tin and enamel. If the catalyst comprises two or more metals, such as a first metal and a second metal, the first metal may be used in an amount of from 0.1 to 10% by weight, such as from 0 J to 5% by weight, or from 〇1 to 3 by weight. %. The second metal is preferably used in an amount of from 2 to 9% by weight, for example from 〇1 to 1% by weight, or from 0.1 to 5% by weight. For a catalyst containing two or more metals, the two or more metals may be alloys with each other or may include a non-alloy metal solution or mixture. The preferred metal ratios may vary slightly depending on the type of metal used in the catalyst. In some embodiments, the molar ratio of the first metal to the second metal is preferably 1 〇: 丨 to 丨: 1 〇, for example: 4:1 to 1:4, 2:1 to 1: 2, 1.5:1 to 1 : 1.5, or U: 丨 to! : U. The catalyst may also include a third metal, which may be selected from any of the first or second metals listed above as long as the third metal is different from the first and second metals. In a preferred aspect, the third metal is selected from the group consisting of: inscriptions, stems, sentences, copper, zinc, tin, tin, and antimony. More preferably, the third metal is selected from the group consisting of cobalt, palladium and rhodium. If present, the total weight of the third metal is from 5 to 4% by weight, for example from 0.1 to 3% by weight, or from 0.1 to 2% by weight. In addition to one or more metals, a typical catalyst further includes a support or a modified support body. This means that the support body comprises a support material and a support modifier, the modifier is adjusted The acidity of the support material. The total weight of the support or the modified support is preferably from 75% by weight to 99.9% by weight based on the total weight of the catalyst, for example, from 78% by weight to 97% by weight, or from 80% by weight to 95% by weight. In a preferred embodiment using a modified support, the 201127793 support modifier contains a halo of from 0.1% to 50% by weight based on the total weight of the catalyst, for example from 0.2% to 25% by weight, 〇·5 From wt% to 15% by weight, or from 1% by weight to 8% by weight. Suitable support materials can include, for example, a stable metal oxide based support or a ceramic support. Preferred support bodies include ruthenium-containing support, such as ruthenium dioxide, oxidized stone shi / oxidized ming, ΙΙΑ 梦 梦, such as hemite acid, pyrolytic cerium oxide, high purity cerium oxide and mixture. Other supports include, but are not limited to, iron oxide, aluminum oxide, titanium dioxide, zirconium oxide, magnesium oxide, carbon, graphite, high surface area graphitized carbon, activated carbon, and mixtures thereof. In ethanol production, the support of the catalyst can be modified with a support modifier. Preferably, the support modifier is a low volatility or non-volatile modifier. Such an inotropic modifier, for example, may be selected from the group consisting of: (i) soil-measured metal oxides, (ϋ) alkali metal oxides, (out) alkaline earth metal hexanoate, (iv) metallographic bias Oxalate, (v) periodic table family metal oxide, (vi) periodic table lanthanide metal bismuth citrate, (νϋ) periodic table lanthanide metal oxide '(viii) periodic table nig group metal bismuth citrate a group of salts, and mixtures thereof. Other types of modifiers, including nitrates, nitrites, acetates, and lactates, can also be used in embodiments of the present invention in addition to the oxides and metasilicates. Preferably, the support modifier is selected from the group consisting of oxides and metasilicates containing sodium, potassium, magnesium, calcium, strontium, barium, and any combination of the foregoing. Preferably, the support modifier is calcium citrate, more preferably calcium metasilicate (CaSi〇3). If the support modifier comprises a sulphuric acid, preferably at least a portion of the calcium sulphuric acid is in the form of a crystal. The preferred oxidized alternative material is a 138 high surface (HSA) dioxide. Eve catalyst carrier (Sdnt-Gobain NorPro). The SS6U38 dioxide dream contains about 5% by weight of the south surface area of the dioxide; the surface area is about MO square meters per gram; the median impurity is about 12 nm measured by the dead-pore analyzer, and the average pore volume is about 1 G cubic centimeter. And the packing density is about 352 gram / cubic centimeter (22 broken / cubic suction). The preferred cerium oxide/alumina support material is 仏16 〇 dioxide (e.g., (10) 咏 = =), has a nominal diameter of about 5 mm, a density of about 62S62 g/ml, and an absorbance of about 〇 583 ^ water. / gram of support, surface area of about (10) to 175 square meters / gram, and pore volume of about (10) 9 201127793. Those skilled in the art know that the support material is selected such that the contact medium is in the process of forming ethanol. With appropriate activity, selectivity and stable strength. The metal of the catalyst can be dispersed throughout the support, coated on the outer layer of the support (like an egg shell) or on the surface of the support. The catalyst composition of the present invention is preferably obtained by impregnating a metal with a modified support, but other processes such as chemical vapor deposition may also be used. Such a immersion technique is described in 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. According to one embodiment of the invention, the hydrogenation to acetic acid process can be carried out using a variety of configurations known to those skilled in the art: fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, &quot;insulation&quot; reactors may be used, i.e., little or no need to pass internal piping to heat or remove heat in the reaction zone. In other embodiments, a radial flow reactor or reactor train or a series of distillation column reactors may be used with heat exchange, quenching, or introduction of more feed. Alternatively, a shell and tube reactor having a heat transfer medium can be used. In many cases, the reaction zone can be placed in a vessel or a series of distillation column vessels in which the heat exchanger is interposed. In a preferred embodiment, the catalyst is used in a fixed bed reactor, for example 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 or bunk bed reactors can be employed. In some cases, the hydrogenation catalyst can be combined with an inert material to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactants with the catalyst particles. The nitridation reaction can be carried out in the liquid phase or in the gas phase. It is preferred to carry out the gas reaction in the following cases. The reaction temperature may range from 125 ° C to 35 (TC, for example: from 200 ° C to 325 ° C, from about 225 t to 300 ° C, or from 250 ° C to 300 ° C. The pressure ranges from 10 kPa (kPa) ) to 3, _ kPa (about 0.1 to 30 atmospheres), for example: from 50 kPa to 2,300 kPa, or from 10 kPa to 1'500 kPa. The reactants are fed into the reactor "vapor per hour" The space velocity &quot; (GHSV) can be greater than 500/hour, for example: greater than ι, 〇〇〇 / hour, greater than 2, 5 〇〇 / hour, or even greater than 5, 0 〇〇 / hour. In terms of range, GHSV It can be from 50/hour to 5 〇, 〇〇〇/hour 'for example: from 500/hour to 30.000/hour, from 1.000/hour to 1 〇〇〇〇/hour, or from 1,000/hour to 6,500/hour. 201127793 The smelting system is sufficient to overcome the space force of the selected vapor per hour, although the higher pressure is not banned, but not the pressure of _=^ drop: r: 5} 〇〇〇 / ^? Although per mole of acetic acid The reaction consumes two moles of hydrogen, and the production one is in the feed stream. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2 to 1: 1〇〇, preferably the molar ratio of hydrogen to acetic acid is greater than 2: 丨, for example: greater than 1 to 1. 1. Contact or residence time (resideneetime) is also very different = 8.1. Medium, reactor, Temperature and Lili change *. Typical contact time * from , the amount 'touches for more than a few hours, if you let the bed outside the bed, the boat time is at least 0" seconds and 100 seconds For example, from 〇3, 3 sec. King 8 sec or 0.4 to =: Γ acetic acid and hydrogen, possibly from any suitable source, including natural hydrazine, petroleum, coal, biomass, etc. For example, Through the oxidation of the apex, the oxidation of ethylene, the oxidative fermentation, and the anaerobic emission, the impurities can be generated due to the stone and natural gas, and the acetic acid and intermediates such as methanol and carbon monoxide are produced from the two processes. The method '6' is causing more and more embarrassing interest ^ In particular, when the price of oil is higher than that of natural gas, 'the synthesis gas derived from any suitable carbon source is good, 0 producing acetic acid may be silk persimmon. For example, @美乡6,232,352 silk grain installed methanol cheap to produce acetic acid 'can be used as a reference to change The methanol plant can significantly reduce or largely eliminate the large capital cost required to produce carbon monoxide in a new acetic acid plant. All or part of the syngas is converted from the methanol synthesis cycle and supplied to the recovery unit for carbon monoxide and hydrogen, which is then used to produce acetic acid. In addition to acetic acid, this process can also be used to make the hydrogen of the application of the present invention. The oxime carbonylation process suitable for the production of acetic acid is described in U.S. Patent Nos. 7,2,8,624, 7,115,772, 7,005,541, 6,657,078, 6,627,770, 6,143,930, 5, 599, 976, 5, 144 068, 5, 026, 908, 5, 001, 259 and 4, 994, 608, the disclosures of which are incorporated herein by reference. Alternatively, ethanol production and sterol carbonylation processes can be integrated. U.S. Reissue Patent No. RE 35,377, incorporated herein by reference, provides a method for the conversion of carbonaceous materials, 11 201127793, such as petroleum, coal, natural gas, and biomass, to sterols. This process includes a method of hydrogenating a solid and/or liquid carbon material to obtain a process gas, which is further added to natural gas for vapor pyrolysis to form a syngas. The synthesis gas is converted to decyl alcohol, which is then carbonylated to obtain acetic acid. The process also produces hydrogen as well, and hydrogen can be used in the present invention as described above. U.S. Patent No. 5,821, <RTIgt; In an arbitrary embodiment, the acetic acid delivered to the hydrogenation reaction may also include other acid retardants and anhydrides&apos; as well as acetaldehyde and acetone. Preferably, a 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 can also be hydrogenated in the process of the present invention. In some embodiments, a drum acid, such as propionic acid or an anhydride thereof, may be advantageous for the production of propanol. Alternatively, acetic acid in vapor form can be removed from the flash column of the methanol carbonylation unit and used directly in the form of a crude product, as described in U.S. Patent No. 6,657,078, the disclosure of which is incorporated herein by reference. Crude vapors can be fed directly into the ethanol synthesis reaction zone without the need to condense acetic acid and light ends or remove water, saving overall processing costs. In an embodiment of the invention, acetic acid may be vaporized at the reaction temperature, and then the evaporated acetic acid is fed with undiluted or hydrogen gas diluted with a relatively inert carrier gas such as nitrogen, argon, helium, carbon dioxide or the like. In order to carry out the reaction in the gas phase, the temperature in the system should be controlled not lower than the dew point of acetic acid. In one embodiment, acetic acid can be vaporized at the boiling point of the hydrogenation reactor operating pressure, and then the acetic acid can be further heated to the reactor inlet temperature. At temperatures below the boiling point of acetic acid, acetic acid passes through the gas, other suitable vapors or their age-old lions are in a vapor state, so that the acetic acid system can be added with gas, and then the mixture is heated until the temperature of the reaction port. Preferably, at a temperature equal to or lower than 12 yc, hydrogen and/or recycle gas is passed through the acetic acid to transfer the acetic acid to the mu' followed by heating and combining to evaporate n to the reaction stomach population temperature. In particular, 'hydrogenation of acetic acid can achieve good conversion and good ethanol selectivity and yield. For the purposes of the present invention, the term "conversion" refers to the ratio of the conversion of acetic acid to a compound other than acetic acid in the feed. The conversion is expressed as a percentage of the moles of acetic acid in the feed. The conversion rate can be 10/above, for example: at least 20%, at least 4%, at least 5%, at least 60% 'at least 7% or at least 嶋. Although the catalyst has a high conversion rate, it is

S 12 201127793 言 ί ί ί ί ί 〇 或 或 或 或 或 或 或 或 , , , , , , , , , , , , , , , , , 。 。 。 。 。 。 。 。 。 。 In many cases, this is easy when the cup is er. (4) Appropriate _ «Dedication A 敝 柯 补 补 补 补 补 补 补 补 补 补 补 补 补 补 补 补 补The rate of conversion is based on the percentage of acid. Applicants for each type of compound converted from acetic acid have a selectivity of 立立, and the rate of conversion is not I. For example: If 50% by mole of acetic acid is converted to ethanol, we mean that the selectivity of ethanol is 观' The catalyst has a selectivity to ethoxylate of at least 6%, such as at least 7%, or at least 80%. The term "ethoxylate" as used herein specifically refers to ethyl ethoxide and ethyl acetate. Preferably, the selectivity for ethanol is above 8%, for example, at least 8 picks or at least 88%. In embodiments of the present invention, products which are preferably preferred, such as methane, ethane and carbon dioxide, have a lower selectivity. The yield of these undesired products is less than 4% 'if less than 2% or less than 1%. It is preferred that these undesired products are not detected during the hydrogenation process. In some embodiments of the invention, the rate of formation is low, typically less than 2%, often less than 1%, and in many cases less than Μ% of acetic acid is converted to alkanes by a catalyst, while alkanes are used as fuel There is not much value outside. ''Yield'' refers to the number of grams of specific product, such as ethanol, per kilogram of catalyst per hour during hydrogenation. Yield yields at least 2 grams of ethanol per kilogram of catalyst per hour, eg: per The kilogram catalyst has at least 400 grams of ethanol per hour or preferably at least 6 grams of ethanol. In terms of mass, the yield is preferably from 2 to 3,000 grams of ethanol per kilogram of catalyst per hour. For example: 400 to 2,500 grams or 600 to 2,000 grams of ethanol. In various embodiments, the crude product obtained by the hydrogenation process typically includes unreacted acetic acid, ethanol prior to any subsequent processing, such as purification and separation. And water. The term "crude" as used herein refers to any composition comprising from 5% by weight to 70% by weight ethanol and from 5% by weight to 35% by weight water. In some typical embodiments, the crude product comprises ethanol, The content is from 5% by weight to 70% by weight based on the total weight of the crude ethanol product, for example, from 1% by weight to 60% by weight, or from 15% by weight to 50% by weight, based on the total weight of the crude ethanol product. Preferably ethanol is crude Containing at least 10% by weight of ethanol, at least 15% by weight of ethanol or at least 20% by weight of ethanol. The crude ethanol product will generally further comprise unreacted acetic acid, depending on the conversion, for example, less than 90% by weight, for example, less than the weight 8〇% 13 201127793 or less than 70% by weight. In terms of range, the unreacted acetic acid content is from 〇 to 90% by weight, for example: from 5 to 80% by weight, from 15 to 70% by weight, from 20 to 70% by weight Or from 25 to 6 S wt%. Since water is formed in the reaction process, the crude ethanol product generally comprises water, for example, the content is from 5% by weight to 35% by weight, for example, from 1% by weight to 30% by weight or 10% by weight. % to 26.% by weight. Ethyl acetate may also be produced by hydrogenation or by side reaction. In these embodiments, the crude ethanol product comprises ethyl acetate in an amount from 〇% to 20% by weight 'eg: from 〇% by weight to 15% by weight, from 1% by weight to 12% by weight, or 3% by weight to 1% by weight. Acetaldehyde may also be produced by side reactions. In these embodiments, the crude ethanol product comprises acetaldehyde, Its content from 〇 Amount % to 1% by weight 'for example: from 0% by weight to 3% by weight, from 0.1% by weight to 3% by weight, or from 0.2% by weight to 2% by weight &quot;Other ingredients, for example: acetals, esters Classes, ethers, aldehydes, _s, alkanes, carbon dioxide 'if detectable, the total content may be less than 1% by weight, for example: less than 6% by weight, or less than 4% by weight. In general, the ethanol crude composition may include other ingredients in an amount of from 0.1% by weight to 1% by weight, for example, from 0.1% by weight to 6% by weight 'or from 0.1% by weight to 4% by weight. Typical examples of the range are shown in Table 1. Table 1 Composition concentration (% by weight) of crude ethanol product Concentration (% by weight) Concentration (% by weight) Concentration i (% by weight) Ethanol 5 to 70 10 to 60 15 to 50 25 to 50 Acetic acid 0 to 90 5 to 80 15 to 70 20 to 70 water 5 to 35 5 to 30 10 to 30 1 to 26 ethyl acetate 0 to 20 0 to 15 1 to 12 3 to 10 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 - Figure 1 shows hydrogenation according to an embodiment of the present invention The gasification system 100 for separating ethanol and acetic acid from the crude reaction mixture. System reaction zone 100 includes reaction zone 101 and vapor zone 102. Reaction zone 101 includes a reactor 103' hydrogen feed line 104 and an acetate inlet line 105. The distillation zone 102 includes a flash column 106 'the first distillation column 1〇7, and the second steaming tower 1〇8, 201127793 are fed through the hydrogen feed line 1G4 and acetic acid respectively; the ^__ is established in the turn 111 The vapor feed stream is directed to reaction 15 03. In one embodiment, the hydrogen feed line 104 and the acetic acid feed line 105 can be a human evaporator 11G, for example, containing hydrogen and acetic acid in one stream. In the pipeline. The temperature of the steamed h feed stream is preferably from 100 ° C to 35 (TC, for example: from 120. (: ΐ 31 2 c' or 150. to 300 oc. Any non-evaporating feed will move up from the evaporator 110 Membrane mounting = riding can be re-recycled. In addition, Lai 1 indicates that the line 111 is introduced to the top of the reactor, and the line 111 can be introduced into the side, upper or bottom of the reactor 1G3. Further modifications and additional components of the reaction Q 101 As described below, the reactor 103 contains a catalyst for nitriding of a neon, preferably acetic acid. In an implementation ff*, 'or multiple guard beds (not shown) may be used to protect the catalyst from In contact with the poison or badness contained in the material or the recirculating ring towel. This _ guard bed can be used in a vapor or liquid stream. Suitable guard bed materials are known in the literature, including, for example, carbon ^ fossil In the case of an oxygen shirt, or a resin, the guard bed medium is used to capture a particular species, such as sulfur or i. In the hydrogenation process, it is preferred to continuously remove the crude stream from the reaction $ ι 3 via line 112. The crude product stream can be condensed and sent to the flash column 1〇6, which in turn provides a vapor stream and a liquid stream. In an embodiment , flash tower 1 〇 _ temperature from to C, for example: from Huan to WC or 100 〇 c to 35 〇〇 c. In one implementation, the pressure of the flash tower 106 is preferably from 50 kPa to 2 000 kPa, for example: from 75 kPa to 1,500 kPa or from 100 to !, _ kPa. In a preferred embodiment the temperature and pressure of the flash column 106 are similar to the temperature of the reactor 1 〇 3 and The vapor stream escaping from flash column 106 may include helium and hydrocarbons which may be removed and/or returned to reaction zone m via line 113. As shown in Figure i, the vapor stream is returned Partly via compressor 114, with hydrogen feed to evaporator 11 (^ removes the liquid from flash tower 106 as a feed composition, through line 115 to the first steaming plant. The steaming tower is also known as the acid separation steaming tower. The content of the piping us is usually roughly the same as that obtained directly from the reactor, and can be practically also characterized as a crude ethanol product. However, the feed in line 115 Preferably, the composition is substantially free of hydrogen, carbon dioxide, methane and ethane, which are removed by flash column 1〇6. The typical composition is listed in Table 2. It should be understood that the line 115 may contain other phase-out ingredients, 15 201127793 as in the feed ingredients, ethanol, acetic acid, ethyl acetate, acetaldehyde, acetal, other esters, other esters, Ethers and other alcohols Table 2 Feed composition concentration (% by weight) - 10 to 60 5 to 80 5 to 30 0.001 to 15 0.001 to 3 0.001 to 2 0.0005 to 〇.〇$ &lt;0.005 &lt; 0.005 &lt;0.005. To 70 &lt; 90 to 35 &lt; 20 &lt; 10 &lt; 5 &lt; 5 &lt; 5 &lt; 5 &lt; 5 concentration (weight _ 15 to 5 (Γ 15 to 70 10 to 30 1 to 12 0.1 to 3 0.005 To 0.001 to 0.03 &lt; 0.001 &lt; 0.001 &lt; 0.001 The amount of the table towel below (&lt;) _ is preferably broken, if present, may be present in a trace amount, or the weight may be more than 0.0001%. The main secret of the waste in the feed group; ^ diethyl secret (DEA, DiethylAeetal, also referred to as sec secret), which is a by-product of the reaction between the two kinds of ethyl alcohol - other narrowing classes such as ethyl propyl Contraction, ethyl radical shrinkage and its semi-shrinkage may also exist. The "others" in Table 2 may include, but are not limited to, ethyl acetate, acetic acid &quot;, isopropyl acetate, n-propyl acetate, butyl acetate or a mixture thereof. The "fine" in Table 2 may include Not limited to B-mystery, methyl ethyl _, isobutyl ethyl hydrazine or mixtures thereof. Table 2, "Other alcohols, may include, but are not limited to, methanol, isopropanol, n-propanol, n-butanol or mixture. Feed composition 'for example: line 115 may comprise propanol, such as isopropanol and / or n-propanol, the content of which is from 0.001 to 0.1% by weight, from 0 001 to 〇〇 5% by weight or 〇 to 〇 weight j should be understood 'These other ingredients can be taken from here, bribes or residual logistics', and will not be stated here unless otherwise stated. = the acetic acid content in the line 115 is less than 5% by weight, then the acid separation steaming ι〇7 can jump = the line 115 can be directly introduced into the second steaming tower 1〇8, which is also referred to herein as the light museum steaming tower. In the τγ J ^ mode, the pipeline 115 is introduced into the lower part of the first steaming tower 1G7, for example, a low heart is one. In the first steaming tower 1〇7 towel, unreacted acetic acid, 201127793 part of the water, and other heavy fractions, if present, will be removed from the composition in line 115, preferably continuously removed as a residue Things. Some or all of the residue may be returned by line ι6 and/or re-reacted to the reaction zone icu. The first-Pagoda 1G7 also forms the tower persuasion to be retrieved by the tube ^ 117, condensed and refluxed, for example: its reflux ratio from 1 〇: 1 to 1: 1 〇, for example. 3 : 1 to 1: 3 or from 1 : 2 to 2 : 1. Any distillation column 1〇7, 108, 1〇9 or 123 in Fig. 2 can be any distillation column which can be made. Preferably, the distillation column comprises a tray distillation column having 1 to 15 Torr trays, for example, having 10 to 100 trays, 20 to 95 trays or 30 to 75 trays, and may be sieve trays. Fixed valve trays, moving valve trays, or any suitable design known in the literature. In other embodiments, a packed distillation column can be used. For the filling of distillation two, both structured packing and loose packing can be used. These trays or packings may be arranged in a continuous distillation column or in two or more distillation columns, so that the vapor enters the second seat from the first seat and the liquid enters the first seat from the second seat. and many more. The associated condenser and liquid separation tanks associated with each distillation column can be any conventional arrangement and are simplified in Figure 1. As shown in Figure 1, heat can be supplied to the bottom of each distillation column or the bottom stream can be circulated through a heat exchanger or reboiler. Other types of reboilers, such as internal reboilers, may also be used in some embodiments. The heat supplied to the reboiler can be generated from any process, and the process can be integrated with the reboiler or with an external heat source, such as a heating chemical reduction. Although there are only reactors and a flash column as shown in the first embodiment, additional reactors, flash towers, condensers, heating elements, and other components can be used in some embodiments of the invention. The skilled artisan is aware that various condensers, pumps, compressors, reboilers, drums, valves, connectors, separation vessels, etc., which are typically employed in a chemical process, may also be combined and used in the process of the present invention. The temperature and pressure used in the distillation column may vary. In terms of practical problems, although in some embodiments subatmospheric pressures and superatmospheric pressures can be used 'but the pressures typically used in these areas range from 1 〇 to 3, 〇〇〇 kPa . The temperature in the different zones is generally between the boiling point of the removed distillate composition and the removed residue composition. Those skilled in the art will recognize that the temperature at which a distillation column is operated is dependent on the composition of the material at that location, and the pressure of the distillation column. In addition, depending on the size of the production process, the secret rate may be older; ^, as the silk secret, may be generally expressed as a weight ratio of 17 201127793 feed. When the distillation column 107 is operated at a standard atmospheric pressure, the temperature of the residue in the line 116 discharged from the distillation column 1〇7 is preferably from 95 ° C to 120 ° C. (:, for example: from l〇5°C to 117. (: or 11〇. (: to 115°0 from the steam tower 1〇7 discharge line in the saturated material temperature is preferably from 7〇〇c to 110. &lt;: 'For example: from 750C to 950C or 80. (: to 90.) In other embodiments, the first distillation column 107 has a pressure ranging from 〇.1 kPa to 510 kPa, for example: from 丨 thousand Palladium to 475 kPa or from 1 kPa to 375 kPa. The typical composition of the first distillation column 1〇7 distillate and residue composition is shown in Table 3 below. It should be understood that the museum and The residue may also contain other ingredients not listed, such as ingredients in the feed. For convenience, the distillate and residue of the first distillation column may also be referred to as "first distillate" or "First residue." Distillates or residues from other steaming towers may also have similar numerical modifiers, second, third, etc., to distinguish each other, but such modifiers should not be construed as requiring any particular Separation order. Table 3 First distillation column concentration (weight 遒; ff heavy ( concentration (% by weight) distillate ethanol 20 to 75 30 to 70 40 to 65 water 10 to 40 15 to 35 20 to 35 acetic acid &lt; 2 0.001 to 0.5 0.01 to 0.2 ethyl acetate &lt; 60 5.0 to 40 10 to 30 acetaldehyde &lt; 10 0.001 to 5 0.01 to 4 acetal &lt; 0.1 &lt; 0.1 &lt; 0.05 C _ &lt; 0.05 0.001 to 0.03 0.01 to 0.025 Residual acetic acid water 60 to 100 70 to 95 85 to 92 &lt; 30 1 to 20 1 to 15 Ethanol &lt;1 &lt; 0.9 &lt; 0.07 As shown in Table 3 Without being bound by theory, it is surprisingly surprising to find that any amount, such as greater than 0·00〇5 wt%, is found in the feed (a crude ethanol product) introduced into the acid separation steam column (first distillation column 107). The acid will decompose in the distillation column. If not theoretically bound, the acetal can be hydrolyzed in the first distillation column 107 to form the corresponding alcohols and aldehydes. 201127793 Reacts in line 112 according to different reaction conditions The crude product taken out of the vessel 1〇3 includes ethanol, acetic acid (unconverted), ethyl acetate and water. After the reactor 103 is discharged, the non-equilibrium catalytic reaction may occur between the components contained in the crude ethanol product until it is added. To the flash tower 106 and/or the first distillation column 107&lt;) The crude ethanol product should be promoted to a balance between ethanol/acetic acid and ethyl acetate/water as shown below.

EtOH + HOAc t; EtOAc + H20 is temporarily stored in the storage zone before it is introduced into the distillation zone 102, for example, in the case of a storage tank, it may encounter an extended residence time. In general, the longer the residence time between the reaction zone 1〇1 and the distillation zone 1〇2, the more cool acid is formed. For example, when the residence time between the reaction zone 1〇2 and the steaming zone 102 is greater than 5 days, more ethyl acetate is formed, at the expense of ethanol. Therefore, shortening the residence time between the reaction zone 1〇2 and the distillation zone 1〇2 is generally advantageous for the maximum amount of ethanol formation. In the "embodiment", a storage tank (not shown) is placed between the reaction zone 1〇2 and the distillation zone 102 to temporarily store the liquid component from the line 115 for up to 5 days, for example, up to a day, or at most hour. In a preferred embodiment, the storage tank for T is used, and the condensed liquid is fed directly to the first steaming tower 1〇7. In addition, the rate at which the non-catalytic reaction occurs can be increased, for example, in the line us, the temperature of the crude product increases. These reaction rates can be particularly problematic when the temperature exceeds the pit, such as more than 4 〇〇 c, or more than 5 Torr. Thus, in one embodiment, the temperature of the liquid component in any of the storage tanks 115 is turned lower than the thief, such as below the thief or below. One or more cooling devices can be used to reduce the temperature of the liquid in line 115. As noted above, a reservoir (not shown) can be placed between reaction n 101 and evaporation zone 102 to temporarily mechanically impart the composition of the components from line 115, for example from 丨 to 24 hours, optionally at about 21 °C. The temperature corresponds to the amount of ethyl acetate formed from 〇〇1% by weight to 〇% by weight. In addition, the rate of non-reverse anti-return can increase with the temperature of the (four) product. For example, the temperature of the medicinal product can be increased by about G.G1% by weight to about _% by weight per hour. Therefore, in the embodiment, the temperature of the liquid component in the crucible line 115 or any storage tank is maintained at a temperature lower than 201127793 21 ° C, such as lower than 4 ° C, or lower than -10 T β may be beneficial to ethanol in First steaming tower In addition, it has now been found that the above equilibrium reaction is also the formation of the top region of 107.顾出物 &gt; The first steaming tower 1〇7 tower top out of the logistics, arbitrary condensation and reflux, such as the first = indicating the preferred stream ratio is i: 5 to 1Q: i. In the line 117, it is preferred to include ethanol, acetic acid and water, and other impurities f, which are difficult to separate due to the formation of a binary azeotrope and a three 7G azeotrope. The third product of the pipeline 7 is led to the first steaming tower, which is also referred to as "light sputum steaming scale"), preferably to the middle portion of the second steaming valve 108, such as the middle half or the middle A three-point example is given. 'When the steaming tower uses a 25-tray steaming tower that does not use water as an extractant, the pipeline 117 introduces the tray 17. Alternatively, part of the first - proud product may be introduced into the second steaming tower 108 and the other part of the first tank may be introduced into the ion exchange resin reactor bed 13 to hydrolyze the secret in the first output, such as the second _ Show. In another embodiment, it is not shown that all of the first-causes are introduced into the ion-removing reactor bed and then sent to the second distillation column. In the other - real money towel, Xuan __ anti-filament bed (not old), can be set in the first steam: tower caught. Preferably, in these embodiments, the ion exchange resin reactor bed is placed and 115 is fed to the point of introduction of the first steam column 107. The internal ion exchange resin reactor bed can also be used in one or more other distillation columns. In the embodiment, the second fine column 1G8 may be an extractive distillation extracting agent such as water, possibly adding · distilling · 1G8. Water, used as an extractant, can be obtained from an external source or from one or more other distillation column internal recovery/recycling lines. The second steaming tower 108 can be a tray steamer tower or a filling tower. In one embodiment the second steaming column 108 is a tray steaming tower&apos; having a 5 to 7 inch tray, for example: from 15 to % trays or from 20 to 45 trays. Although the temperature and pressure of the second steaming tower 1G8 may vary, the temperature of the residue discharged from the second steaming tower outlet line 118 at atmospheric pressure is preferably from 9 〇〇c, for example: from 70 ° C to (four) or 80 ° C to 90. The temperature of the distillate discharged from the second steaming tower 1 8 to the outlet 12 〇 is preferably 50 〇C to 90. (: For example: from 60^ to 8〇〇c or 6〇〇c to 70° C. The second distillation column 108 can be operated at atmospheric pressure. In other embodiments, the pressure range of the second distillation column 108 is 201127793 From 0.1 kPa to 510 kPa', for example: from 1 kPa to 475 kPa or from 1 kPa to 375 kPa. The typical composition of the second distillation column 1 〇8 distillate and residue composition is listed below. Table 4. It should be understood that the distillate and residue may also contain other unlisted ingredients, such as ingredients in the feed. Table 4 Second Distillation Column Concentration (% by weight) Concentration (% by weight) Concentration ( Weight%) 10 to 90 25 to 90 50 to 90 1 to 25 1 to 15 1 to 8 1 to 25 1 to 20 4 to 16 &lt; 30 0 to 15 〇·〇1 to 5 &lt; 5 0.001 to 2 0.01 To 1 30 to 70 30 to 60 30 to 50 20 to 75 3 to 70 40 to 70 &lt; 3 0.001 to 2 0 001 to 0.5 &lt; 0.5 to 5^21 to 0.3 0.001 to 0.2 Aldehyde Water Ethanol Acetal Residue Water Ethyl Acetate Acetate Acetic Acid ί ===_ Second Residue. Feeded to the second steaming Na (10): Hydrolyzed to reduce the diethyl ester content. In the embodiment, 'the hydrolysis in the first distillation column 107 is not hydrolyzed at 108. The monocondensation may be carried out in the second residue in the second residue, ethanol to the second take-up 1, for example: at least 6 : 1 , at least 8: Bu, the weight is better, at least 3: In the second residue, the second sample of acetic acid is taken out > 1G. 1 or at least 15: from 1 from, such as: lower than 0.2:1 or less than the weight of 〇.1:1 θ acid vinegar is preferably low. In the embodiment of the extraction column as the extractant, as in the second steaming tower 108, the weight of ethyl acetate in the water distillate is used. The ratio is equal to zero. The second residue in the ethyl acetate is as shown in the second figure, and the second excess line 118 at the bottom of the second distillation column 1〇8 is fed to the third distillation column 1〇9 'It includes ethanol and water, pass,,, °. It is also called "product steaming tower,". More preferably, the second residue in 21 201127793 is introduced into the lower part of the third steaming tower 1〇9, such as the bottom half Or lower two or two. The ethanol recovered from the third distillation column 109 is preferably substantially purified ethanol, and the secret: the road 119 contains azeotropic water. Preferably, the first residue is as follows: for example, the reflux ratio is from 1:10 to 10:1, for example: from 1:3 or from 1:2 to 2: the third residue in the line 121 It is more watery than the Γοο, and the 1GG towel is removed or can be sent back to the system for better material. The third thin tower 1G9 is detailed on the tray tower and is operated under pressure. The temperature of the third substrate discharged from the line 119 is preferably from ^ to "1" c, for example, from 70T to 100〇c or 75〇c to 95〇c. When the third steaming: operating under the magic of the atmosphere, the third residue discharged from the third steaming tower 109 is preferably from the solid to the cockroach, for example, from ah to 丨 (1). C, or sink to = steamed scale 1G9 _ output and _ matter typical composition as shown in Table 5 below and residues may also contain other ingredients not listed, such as: ethanol water acetic acid ethyl acetate water Ethyl acetate ethyl acetate acetic acid Table 5 Third distillation column concentration (% by weight, 75 to % &lt; 12 &lt; 1 &lt; 5 80 to 96 1 to 9 0.001 to 0.001 to 0.1 4 85 to 96 3 to 8 0.005 to 〇. 〇1 〇.〇1 to 3

80 to 1 〇〇 0.001 to 0.5 0.001 to 0.5 0.001 to 0.5 90 to 1 〇〇 0.005 to 〇. 〇 5 0.005 to 0.2 0.005 to 0.2 22 201127793 f Multiple _ flow removeable system (10) t of any - steamed scale (10) and And/or ι〇9 is used to remove impurities from the third steaming tower 109 in at least one side of the application. Impurities can be removed and/or retained within the system 1〇〇. The H3 Middle 3 product may be further purified using one or more additional points: Jingguan Tower) or molecular sieve to form an anhydrous turbulent flow: that is, "completed anhydrous ethanol product''. Return to the second steaming 1G8 The second shaft in the line 12G, preferably, is refluxed, for example, having a reflux ratio of from 1:1 〇 to 1 〇: 1, for example, from ι:5 to U or /.1 to 3.1. As shown in Fig. 1, the second residual can be removed or recovered into the anti-ship. In the embodiment, as shown in Fig. 2, the pipeline 12 is processed in the fourth steaming (2). The shaft pipe 12G jt is mainly composed of acetic acid B. The 'acetate B · f is impure and still contains other components. These additional components can be treated and removed from the second distillate. 100 is similar to the first!, but the second museum is fed into the fourth steamer 123 through the pipeline (9), which is also called the removal of the brain tower. In the fourth tower (2), the second museum is separated. It becomes the fourth library in the pipeline 124, which includes the fourth residue of the pipe 125, which includes the ethyl acetate. The fourth museum is preferably produced. The reflux ratio is from 1:20 to 20:1, for example: from 丨:15 to 15: 丨 or 丨:1〇 to i〇: i is refluxed' and part of the rms is returned to reaction zone 1 (n. For example: The fourth remaining product may be combined with an acetic acid feed, added to the hairdresser 11G, or directly added to the reactor 1 () 3. As shown, the fourth distillate is fed together with the acetic acid fed into the line 105. Evaporator 11 〇. If not theoretically bound, because acetaldehyde can be hydrogenated to form ethanol, the acetaldehyde-containing stream is sent back to the reaction zone, increasing ethanol production, and reducing the production of by-products and waste in another implementation (Figure ^ not shown Where acetaldehyde can be collected and utilized, with or without further purification, to produce useful products including, but not limited to, n-butanol, 1,3-butanediol, and/or crotonaldehyde and its derivatives. The fourth residue of distillation column 123 can be purged through line 125. The fourth residue consists essentially of ethyl acetate and ethanol, which may be suitable as a mixture for the solvent, or for the production of S. In the preferred embodiment In the way, 'the acetaldehyde is removed from the second museum of the fourth fine tower 123, so that the fourth steaming There is no detectable amount of acetaldehyde in the column 123 residue. The fourth distillation column 123 is preferably a tray distillation column as described above, preferably operating at a pressure higher than atmospheric pressure 23 201127793. In the embodiment, the pressure From 12Q kPa to 5 kPa, for example. From 200 kPa to 4,500 kPa, or 400 kPa to 3, _ kPa. In the formula, the first shouting 123_ can be higher than other _ The I side is discharged from the fourth steamer 123 via the line 124.

No〇c,^ 7〇x ^ 100〇c , 75〇c ^ 95〇c 〇 J

The temperature of the discharged residue is preferably from 7QT to 115. Oh, for example. From, 8〇: C =. (: 'Or W to say that the typical composition of the _ tower 123 post and precursors is listed in Table 6 〇 It should be understood that the cousins and residues may also contain unlisted, such as ingredients in the feed. Eight he took the table 6 concentration of the fourth distillation column (weight ° / 〇) distillate acetaldehyde 2 to 80 ethyl acetate &lt; 90 ethanol &lt; 30 water &lt; 25 acetal &lt; 1 residue ethyl acetate 40 to 1 〇〇 Ethanol &lt; 40 water &lt;25 acetaldehyde &lt;1 acetal &lt;1 (% by weight) skin (Pange 0 / Λ 2 to 50 5 to 40 30 to 80 40 to 75 0·001 to 25 0.01 to 20 0-001 to 20 0.01 to 15 &lt; 0.05 &lt; 0.001 50 to 1 〇〇 60 to 100 α 〇〇 1 to 30 0 to 15 0.001 to 20 2 to 15 0.001 to 0.5 Not detectable &lt; 0.05 &lt; 0.001 ri; above, in an embodiment, the ion exchange resin reactor j may be included in the process as shown in Fig. 2, and the external ion exchange reactor bed (not shown) is also "立立; The first take-up of the part, for example, the lion reaction can be passed through the pipeline 131. The ion exchange resin reactor bed 130 is preferably a Zf mesh bed 4 Road 131_A is hydrolyzed in reactor bed 130, ^'flow' which includes ethanol and ethylene. The obtained stream, or an aliquot of the stream 'may: (1) return to reaction zone (9), as shown by line i32 (8) Introducing a second steaming hall 24 201127793 Tower 108, as indicated by line 133; (iii) introducing a third distillation column 123, such as line 134 or (iv) a combination thereof, although Figure 2 shows the feed to the bed. The ion exchanger bed 13Q^, however, in some embodiments, all of the first, the output can be sent to the bed separator bed 130. In a preferred embodiment, the resulting flow is via a line m is returned to the first steaming tower, and the completed ethanol composition obtained by the process of the invention is preferably comprised of from 75 to 9% by weight of ethanol 'for example: from 80 to 96 % by weight, or 85 to 96% by weight of ethanol, based on the total weight of the finished ethanol composition. Typical ethanol composition compositions are listed below in Table 7. Composition Table 7 Completed Constituent Concentration of Ethanol (% by weight) Concentration (weight 0/〇) Concentration (% by weight) Ethanol 75 to 96 80 96% to 96 water &lt;12 1 to 9 3 to 8 acetic acid &lt;1 &lt; 0.1 &lt; 0.01 ethyl acetate &lt; 2 &lt; 0.5 &lt; 0.05 acetal &lt; 0.01 &lt; 0.005 &lt; 0.05 propyl &lt;0.01 &lt; 0.005 &lt; 0.05 isopropyl alcohol &lt;0.5 &lt; 0.1 &lt; 0.05 n-propanol &lt;0.5 &lt; 0.1 &lt; 0.05 The ethanol finished product composition of the embodiment of the present invention is suitably used in various applications, including Fuels, solvents, chemical materials, pharmaceuticals, detergents, disinfectants, hydrogenated transport or consumer goods. In fuel applications, denatured ethanol compositions can be blended with gasoline for use in motor vehicles such as automobiles, boats and small piston engine aircraft. In non-fuel applications, denatured ethanol compositions are useful as solvents, detergents, disinfectants, coatings, inks, and pharmaceuticals for cosmetic and cosmetic preparations. The ethanol finished product composition can also be used as a process solvent for pharmaceutical products, food preparations, dyes, photochemicals, and latex processing. The ethanol finished product composition can also be used as a chemical raw material to manufacture other chemical materials such as vinegar, 25 201127793 propylene „acetic acid ethyl vinegar, ethylene, glycol ethers, ethylamines aldehydes, higher alcohol H1 alcohols. Warm Bingcai, the ethanol finished product composition can be dehydrated to produce ethylene by acetic acid or by reacting with the polyethylene. The known hydrazine can dehydrate the ethanol, as described. U.S. Patent Application Publication No. 2_003_ and Measured/003_, the entire contents of which are hereby incorporated by reference in its entirety in the the the the the the the the the the the the the the the the the the the the the the the the the the the the Nano's preferred stagnation stone comprises a dehydration catalyst selected from the group consisting of mordenite, ZSM _ mouth 5, sea stone X and zeolite gamma. Zeolite &amp; For example: described in U.S. Patent No. 2 No. 244 and Foshan Υ is described in U.S. Patent No. 3, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in the the the the the the the the the Distillation process. Example Μ 5 Implementation Examples 1-9, reported in Table 8 'Measure 彳丨人第' and 2 earn separation columns, for example: First distillation column 107, acetal content in the feed, and acetal in the distillate and residue Contains, The value in Table 8 is in grams per minute, and it can be seen that the acetal content is significantly reduced in the acid separation distillation column. No acetal was found in the residue. 26 201127793 Reducing acetal content reduction Example 1 2 3 4 5 6 7 Subsequent knife difference (g/min) residue (g/min) 0 0 0 0 0 0 0 U.ZDo 0.009 0.010 0.011 0.005 0.005 0.003 0.007 0.345 0.323 0.091 0.079 0.085 0.314 9 0.315 0.337 0.008 0 0.012 0 Examples 10-15, reported in Table 9, also measured the amount of acetal in the feed to the acid separation distillation column and reduced in distillate and residue The content of aldehydes. The numerical unit of Table 9 is % by weight, and the content of the acetal in the acid separation vapor column is remarkably reduced. No acetal was found in the residue. Table 9 Reduction of acetal content in the first distillation column Example Feed (% by weight) Distillate (% by weight) Residue (% by weight) 10 0.3958 0.0438 0 .11 0.0792 0.0047 0 12 0.448 0.03 0 13 0.0898 0.0027 0 14 0.7166 0.1161 0 15 0.679 0.151 0 Example 16 A feed containing approximately 4,000 ppm of acetal was fed to a tray 17 of an acid separation distillation column. The content of acetal in each tray of the distillation column was measured. In the tray near the bottom of the distillation column, there is no substantial presence. 27 201127793 Wall ^ 10 2 7 17 22 32 37 42 47 Reduced acetal content in the steaming tower ° - - Contraction (p_ 0 1 68 3 2117 1631 1747 2034 It is to be understood that the various modifications within the spirit and scope of the invention are obvious to the above. The above-mentioned discussion of the relevant knowledge and technical literature of the present invention layer = each implementation of the disclosure can be incorporated herein by reference. The parts of the method and the following various features and/or accompanying patents are all or part of the following. In the description of the foregoing various embodiments, the embodiments may be combined with other embodiments as appropriate, and the familiarity with the field is σ. B b. Furthermore, those who know the ordinary technical literature understand that the previous description of the gossip is for the purpose of closing the scope of the duck. [Simplified description of the diagram] = The following reference to each of the peaches to turn the invention, the number of the marriage The component of the partial _. The circle of the present invention is a flow chart of the hydrogenation system of the real-life ion-exchange resin bed reactor. .

28 201127793 [Description of main component symbols] Code description 100 Nitriding system 101 Reaction zone 102 Distillation zone 103 Reactor 104 Hydrogen feed line 105 Acetic acid feed line 106 Flash column 107 First distillation column 108 Second distillation column 109 Third Distillation column 110 evaporator 111 line 112 line 113 line 114 compressor 115 line 116 line 117 line 29 201127793 code description 118 line 119 line 120 line 121 line 123 line fourth distillation column 124 line 125 Line 130 Ion exchange resin reactor bed 131 Line 132 Line 133 Line 134 Line

Claims (1)

201127793 VII. Patent application scope: 1. A method for purifying crude ethanol product, the steps comprising: forming a crude ethanol product in the presence of a catalyst in a reactor, which comprises ethanol water, ethyl acetate and acetal. Wherein the acetal is present in the first amount; and the at least a portion of the crude ethanol product is separated into the first distillate in the first distillation column, which comprises ethanol, water, ethyl acetate and the second portion, and the first residue It comprises acetic acid, wherein the first amount is greater than the second amount. 2. The method of claim 1 wherein the first portion exceeds the second portion by at least 50%. 3. The method of any of claims 1 and 2, wherein the first portion of the chain is greater than 0·_5 4% by weight, the percentage being at least a portion of the total weight of the crude ethanol product. 4. The method of claim 3, wherein the second amount of shrinkage is less than 5% by weight, based on at least a portion of the total weight of the crude ethanol product. 5. The method according to any one of claims 1 to 4, wherein the condensed chain is selected from the group consisting of diethyl condensed chain, ethyl propyl group, ethyl butyl group and semi-secret thereof . 6. The method according to any one of claims 1 to 5, wherein the first residue is substantially free of acetal. 7. The method according to any one of claims 1 to 6 And including, in the second steaming, separating at least a portion of the first-cause output into a second library, which includes ethyl acetate, and a second residue comprising ethanol and water; and in the third steaming Separating at least a portion of the second residue to become a third library product comprising ethanol, and a third residue comprising water. The method of claim 7, wherein the acetal is hydrolyzed in the second distillation column in at least a portion of the first distillate fed to the second vapor column. 9. The method of any of claims 7 and 8, wherein the third library material is substantially free of acetal. 10. The method according to any one of the preceding claims, wherein the catalyst comprises a metal combination selected from the group consisting of platinum/tin, platinum/rhodium, platinum/ruthenium, diτ, p/chain, throwing ^ , Drill / New Zealand, Cobalt / Chromium, Cobalt / Pair, Move, Copper / Palladium, Record / Ji, Jin / Ji, Shi chain, and nail / iron group. a method for purifying crude ethanol, the steps comprising: hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product comprising ethanol, ethyl acetate, water, acetic acid and acetal; At least a portion of the crude ethanol product becomes the first drug, which includes ethanol, water, ethyl acetate and a reduced route, and a first residue comprising acetic acid; and hydrolyzed at least a portion of the first distillate. 12. The method of claim U, wherein the acid is hydrolyzed in at least a portion of the first extract to produce ethanol and ethylene. A. The method of claim ii, wherein the secret is selected from the group consisting of diethyl ester, ethyl propyl, ethyl butyl, and semi-secret. 14. The method of any of clauses 1 to 13, wherein at least a portion of the first distillate is hydrolyzed in an ion exchange resin reactor bed. K. If applying for full-time (4) Μ 赖 之 , , , , , 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾32 201127793 The method of applying for the __ mm item in the rewards also includes: - the distillation column separates at least part of the first acid vinegar, and the b-th product becomes the second discussion, which includes a residue of vinegar , which comprises ethanol and water; and at least a portion of the second distillation column is separated, and the product becomes a third museum, which includes ethanol and a second residue, which includes water. At least a portion of the first distillate is hydrolyzed in the second distillation column in which the ion exchange resin reactor bed is disposed. 18. The method of claiming the patent scope is described in the first steaming tower. Applying for a patent to touch the pine of the 18th, the coffee in the fourth _ tower separated at least part of the second museum to become the fourth museum, including the road 'and the fourth residue' (four) acetic acid (10) 'the (10) paste __ The method of claim 18, wherein the hydrolyzed portion of the first distillate is introduced into the fourth distillation column. 21. A method of purifying a crude ethanol product, the method comprising: hydrogenating acetic acid in the presence of a catalyst in a reactor to form a crude ethanol product comprising ethanol, ethyl acetate, water, acetic acid and acetal; The crude ethanol product forms a hydrolyzate; and at least a portion of the hydrolyzate is separated in the first distillation column to form a first distillate comprising ethanol, water, ethyl acetate and acetal and a first residue comprising acetic acid. The method of claim 21, wherein at least a portion of the crude ethanol product is hydrolyzed in an ion exchange resin reactor bed. The method of claim 22, wherein the ion exchange reactor bed is located in the first distillation column. The method of claim 21, wherein the secret is selected from the group consisting of diethyl acetal, ethyl propyl acetal, ethyl butyl acetal and its hemiacetal. The method of any one of claims 21 to 24, further comprising: separating the crude ethanol product into a vapor stream and a liquid stream in a flash column, returning at least a portion of the vapor stream to the reactor; and hydrolyzing at least Part of the liquid stream forms a hydrolysate. C 34