SA111320169B1 - Processes for Producing Ethanol from Acetaldehyde - Google Patents

Abstract

The present invention relates to processes for forming an ethanol mixture through the hydrogenation of an acetaldehyde feed stream in the presence of a catalyst. The acetaldehyde feed is composed of acetaldehyde in the presence of at least acetic acid and ethanol. Preferably, the acetaldehyde feed stream is a stream flown by the producer through the vinyl acetate manufacturing process.

Description

-y- Ethanol production processes from acetaldehyde

Processes for producing ethanol from acetaldehyde Full description of the invention Ads Ethanol for industrial use is traditionally produced from petrochemical feed stocks; such as oil, natural gas, and coal; and petroleum derivatives “Jiao oils” or from starchy materials or cellulosic materials ©; Like corn or sugar cane. and traditional methods of producing ethanol from petrochemical feed stocks; be of cellulosic materials; They include water and an acid catalyst of ethylene ¢ methanol homologation and a combination of alcohol ¢ and a Fischer-Tropsch combination The instability in petrochemical prices contributes to feeding stocks and fluctuations in the costs of ethanol produced traditionally. When the prices of oil derivatives rise; And the need for alternative sources for the production of ethanol 0 becomes more necessary for such inventions, so that it becomes an indispensable necessity. dextrin is converted; as well as cellulosic materials; ethanol by fermentation. Fermentation is usually used to produce ethanol as fuel demand or consumption increases. In addition ; The fermentation of starchy or cellulose materials competes with food sources and places restrictions on the amount of ethanol that can result from the use of industrial ethanol. Ethanol 0 is produced by the reduction of alkanoic acids and/or other carbonyls as the group of alcohol-containing compounds has been studied extensively; a variety of combinations of catalysts and catalysts; The operating conditions have been mentioned in this scientific article 0. through

creamy - reducing alkanoic acid; acetic acid so that it often forms with other ethanol compounds or is formed in side reactions. For example; during hydrogenation; Esters are produced with ethanol and/or 85 in the form of water; Ally is hard to find apart. These impurities can limit the production of ethanol, and the process of producing it by trains may require costly and complex purification © to separate impurities from ethanol. Hydrogenation of acetic acid usually produces ethanol and water along with small amounts of impurities with some byproducts. Side. In theoretical maximum selectivity conversion ¢ the raw product ethanol comprises approximately 7/7 of ethanol and A YA of water. in order to form Jal ethanol; Much of the water that resulted in the reaction must (Lely) form ad ethanol. In addition; incomplete conversion; The unreacted 0 acid may remain in the 0"01a"_ crude produced. It is desirable to AY sale these residual acids using vinegar from 01“att”_ the crude product to produce pure ethanol. It is also well known to reduce these acids; hydrogenation of hydrogenate aldehydes aldehydes on its ALLA alcohol. And therefore ; Ethanol may be formed by hydrogenation of acetaldehyde. Typical processes for aldehyde hydrogenation 0 are described in US Patent No. 6? 47 suffocation of the right hand of the slit of the scrotum ¢ of the buttocks of the brain + occlusion » dark 17, s; Sources are already mentioned. For JU; Hydrogenated compounds (crotonaldehyde) may be used to form alcohol 1e. The following references have reported on such type of reactions: Djerboua (1); et al. Yo “on the performance of a highly adedCO/SIO2 catalyst in gas phase hydrogenation of thermal treatments.

EP

(0015) Catalyst Structure Selective Relation “Applied Catalysts General Edition == crotonaldehyde” Catalyst Performance 705002 in Phase Tourounde « Liberkova (Y) 7-177 Element YAY Bit ¢ (YoY) Chemicals :.

CYOV (0016) iii. Enhancing Effect of Zinc; “Applied Catalysts: General: © crotonaldehyde; et al.; ‘Nasogenic Catalyst’: Use of an Oxide Catalyst.” Ammari (4); 701-711 p. 7-77 Text YY (1) (001) J. Catal 'Zn crotonaldehyde/selective hydrogenation of zinc using catalysts' selective crotonaldehyde of 1; et al.; hydrogenation Ammari (©) ale' et al. Consonni (1); aldehydes; et al.; “Selective hydrogenation of Nitta; and 179-166 pp. 48¢ (1444) obtained from silica (cobalt---unsaturated silica catalysts) using catalysts.

XY=4 Same source. (195483) 60 07 p.m. (cobalt chrysotile through ethanol) Even in light of this information, there remains a need to improve processes to produce, which contain a highly efficient hydrogenated acetaldehyde hydrogenation of 0. ethanol from The general invention of the invention is a process consisting of a step by hydrogenation of an ethanol stream This invention relates to processes for producing a first catalyst mixture comprising metals ethanol in the presence of a catalyst to form an acetaldehyde feed mixture one by one The least of the feed streams for silicaceous support and cellulose as an adjuvant is 0

Acetaldehyde contains at least one of the ethanol's acetic acid. And in general; The acetaldehyde feed stream feed includes 4 YO of 7 50 by weight, acetaldehyde of 7 01 by weight, / VO by weight of acetic acid and | or ethanol from the ethanol mixture prepared by the reaction process; Preferably to include 00 to AY by weight of ethanol and 7 to ve by weight of water ;. © less than Yo 7 by weight acetic acid ; and less than 701 weight of acetaldehyde. Overall ; The conversion ratio of acetaldehyde in the acetaldehyde feed stream is La not less than VO / and the conversion of acetic A acid in the acetaldehyde feed stream is La not less than 7 01 It is preferred that the catalyst be completely impure in the conversion of acetic acid y acetaldehyde into ethanol. 0 The catalyst used in the conversion of acetaldehyde and/or acetic acid i to ethanol shall preferably be based on a purity of ethanol of not less than Av 7; For example ; at least 5m 7 68 72 at least − or up to Joao Jae in the last process ¢ a process that includes a step of contact between a mixture of acetic acid y ethylene with oxygen to produce vinyl acetate at least one of the products comprising an acetaldehyde stream; for example due VO; From 7246 to 4964 7 of weight 6621069706. ; Thus, in the hydrogenation process, where the product must contain at least part of the feed stream in the presence of a catalyst to form an ethanol mixture. The by-product stream shall preferably contain at least one evaporative agent with separate feed streams consisting of at least one rammed acetic acid to form a steam feed stream; Which dng reaction into hydrogenation reaction for hydrogenation of ethanol 0 Brief explanation of the drawings

The invention is described in detail below with reference to the attached drawings ¢ where the numbers represent the bent parts. Figure 1: Schematic diagram of the hydrogenation separation system with the presence of the three components according to one of the steps of this invention. © form? : Schematic drawing of the hydrogenation separation system with the presence of the four components according to one of the steps of the present invention. The reactions may have formed ethanol (and water) ¢ by hydrogenation of acetic acid as represented by the following reaction: 0 JR 2H, HO + —- CH OH “Non ’

3 Ye However, with this interaction; Impurities and/or products obtained are frequently produced through side reactions. Where droppers can be used to obtain significant purification to form a formula

Asaat “H_Al-Naqee Lad 0”, the formation of these products reduces the conversion of acetic acid into ethanol. Ethanol can also be produced through acetaldehyde hydrogenation. In Vo the application of the theory; Ethanol is the only product of the hydrogenation of acetaldehyde (aside from small amounts of impurities produced by the side reaction and/or by-products). in these cases; Water is not a catalyst in the production of “ethanol,” as is the case in the hydrogenation of acetic acid. And therefore ; The resources

The - required to remove impurities in the acetaldehyde hydrogenation process is much less than in the acetic acid hydrogenation process. Accordingly, “the processes of this invention have a useful use for the hydrogenation of (ye ethanol WY acetaldehyde) the mixture that (ging) a few impurities of the reaction products. In addition, the hydrogenation of acetic acid is carried out through two reaction steps. © The first step is endothermic and produces acetaldehyde and the second step is the hydrogenation process from acetic to faster and exothermic.Unlike the hydrogenation of 1.ethanol this step is to form acetaldehyde using an endothermic step.As a result, acetaldehyde does not have to be The hydrogenation + acid is a more process, and it may have been carried out at a lower temperature than the acetaldehyde reactor, so the hydrogenation of acetic acid is hydrogenation.

0 In short, this invention is a process for producing an ethanol mixture that includes a step of hydrogenation using an acetaldehyde feed stream to produce an ethanol mixture; Where the mixture of ethanol and methanol contains either or both acetic acid and | or ethanol. Since it was discovered that the addition of acetic acid and | or ethanol to acetaldehyde in a feed stream that unexpectedly improves hydrogenation and increases the conversion of acetaldehyde and thus | ; And in one interaction; The acetaldehyde feed stream comprises one or more

0 of acetaldehyde and at least one of ethanol's acetic acid. Overall ; The feed stream 756 includes a mixture of acetic acids acetaldehyde ¢ which is a mixture of acetaldehyde 5 + ethanol or a mixture of ethanol 5 “acetic acid s ¢” acetaldehyde. and an acetaldehyde feed stream comprising 170 by weight of 7 960 cacetaldehyde (for example, Jad); In the ratio of 790 = #No22 or 46 7 - 7 1 to the weight of the acetaldehyde and plus

yum - acetic acid “acetaldehyde” or “ethanol”  The acetaldehyde feed streams may include additional components  but are not limited to propanoic acid  esters and water. As indicated above » in the interactions; The acetaldehyde feed stream includes acetaldehyde and acetic acid. The hydrogenated materials and 8010 acetic may be under the same conditions as for y-acetaldehyde in this reaction; In addition to acetaldehyde, the feed stream is preferably less than 756 by weight, “acetic acid,” for example; Less than © # wt. or less than cite may be an acetaldehyde feed comprising acetic acid in between 701 wt - AYO wt ; For example Yo 7 to 71 Wt or 7 01 Wot . in the last interaction; The acetaldehyde feed stream contains ethanol 5 acetaldehyde. Preferably ethanol 0 passes through a reaction system that does not substantially change its properties. It is preferable that ethanol does not significantly affect the hydrogenation of acetaldehyde when ethanol is present in the feed in addition to acetaldehyde » and the acetaldehyde feed preferably includes less than ethanol / Vo ; ie + less than 7080 or less than 0 Lov and an acetaldehyde feed optionally comprising ethanol in weight from 7 017 to 75 ; For example, JE; From the weight of Yo Lye 0” or 746 to 7 11 . Usually the goal of the reaction is to get acetaldehyde into the acetaldehyde feed by the products from the vinyl acetate production process. It is usually formed through vinyl acetate sl acetoxylation of ethylene. In this reaction “acetic acid ethylene reacts in the presence of vinyl acetate JS33 oxygen ¢ and in some cases; By-products, acetaldehyde (Jie), may be suitable for the production of catalysts for vinyl acetate ¢ such as those contained in British Patent No.

168; US Patent No. 1 Lacquer Lacquer Lacquer 110704 and ally aforementioned. And in some interactions; The catalyst is made of palladium and gold.” However, in traditional processes, it is made of vinyl acetate. The acetaldehyde is usually separated from the vinyl acetate, which is oxidized to produce acetic acid 5, which is recycled to produce vinyl acetate. © In addition; It may be the reaction of acetaldehyde with anhydrides to produce . ethylidene 35 as shown in US Patent No. 7854741 5 C YEYOVAQ and the explanations given by Jala and in one of the steps of this invention; The acetaldehyde is recovered to form an acetaldehyde feed stream “so that at least eda of it is directed to the hydrogenation reactor for conversion to” ethanol eg Ye; The sia of acetaldehyde in the unhydrogenated vinyl acetate produced from the reaction is used to form the ethanol stream. It is permissible to use the current from the acetaldehyde product containing the aforementioned chemical mixtures to produce vinyl acetate, which includes; at least 40 7 ‎acetaldehyde « eg; Not less than AY or 7954 of acetaldehyde ¢ and the resulting stream preferably includes 740 = 19:4 7 acetaldehyde ¢ on Jun Article No 7 — 79900 acetaldehyde Vo and the resulting streams may contain small amounts from impurities; Percentages of less than 71 or a dil of 0.1, such as: acrolein, methyl acetate, ethyl acetate, methyl formate, crotonaldehyde, propionaldehyde, propionic acid, vinyl acetate, and benzene, and it is preferable to use vinyl acetate by the hydrogenated product stream in the presence of the catalyst which is also Yo effective for the hydrogenation of acetic acid to form ethanol. As a result ¢ the vinyl acetate that may be

- y = before hydrogenation. in these cases; The ethanol and/or acetic acid combined in the product stream may be evaporated prior to the ethanol and/or acetic acid along with the product stream =A = hydrogenation and exposing The product of the vaporized feed stream in the hydrogenation reactor. Also, acetaldehyde; vinyl acetate may be formed in addition and as a by-product of an aggregation process as described in Pat. No. 71/815079; in which acetic acid was produced. Hydrogenation of the © used in the acetaldehyde feed stream referred to earlier.In such reactions; the acetic produced from the acetaldehyde product and the vinyl acetate streams are formed from a mixture of acetaldehyde before the oxidation of ethylene process Hydrogenation It can also be formed in the oxidation of ethylene 80 hydroformylated Jali also in the oxo process in which acetaldehyde acre is produced and thus may produce carbon monoxide and hydrogen. By any acetaldehyde feed stream used to feed the acetaldehyde stream derived from these processes, or both; the feed stream may be ethanol y acetic acids ¢ acetaldehyde and in addition to their anhydrides » carboxylic acids include one or more other components such as acetaldehyde 0 such as carboxylic acids and water; and mix them. Which can be in the presence of ¢ ethyl acetate s ; acetone 0 . propanol; To be useful in producing propanoic acid acetic acid or containing a certain metal. so that, acetaldehyde in some reactions; The catalyst is for a feed stream; If the acid is vinegar. The acetaldehyde catalysts for ope hydrogenation may be the best catalyst for the appropriate hydrogenation, including the first group metals. It is preferable that the catalysts also include one or more of the second group metals ¢ or the third group minerals; or additional minerals. 0 can be selected

the first, second and third metals of any of the following groups VIIB ¢ VIB « ¢ IMB which includes _transition metals ; methyl anthanide; It is the metal of the actinides or the metal chosen from any of the previous groups, and the preferred mineral combinations for some of the ideal (jana) compositions include: platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, © palladium/rhenium, cobalt /palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium, and ruthenium/iron. They are listed among ideal catalysts. In US Patent No. 6048746 0 8274/8950 published in US No. 10997488/7019 and cited above. in the course of interactions; The first metal is determined from a group consisting of: copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten. In other reactions; The first metal is selected from a group consisting of palladium, cobalt, nickel, and ruthenium 0. It is preferable that the first metal be platinum or palladium. due to high demand; So that the first metal includes platinum and the catalyst, and it is preferable that the weight of the platinum be less than 7 © in ; For example ; less than 77; or less than 1 ; or less than Jove and as indicated above; An optional catalyst incorporating group II metals may be used; which may act as a promoter. and if possible; The second metal can be identified from a group consisting of:

Y — \ _ copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel. It is preferable to specify the metal the second from a group consisting of copper, tin, cobalt, rhenium, and .nickel: © and if it is a catalyst comprising two or more metals; For example ; metal of the first and second groups; The primary metal is optional in the catalyst in a ratio of 0 ranging between 1 - 7 01; For example + Zo - 00 . Or vd = 9 7 of the total weight + and the metal of the second is optional in proportions such as b - 01 a v 01-1 7 or vi) - 0 / of the total weight. Catalysts may include two or more metals; And it is in the form of alloys with each other or may 0 - formed from non-alloyed or alloyed metals. The percentage of minerals may vary depending on the minerals used in the catalyst. In some perfect application; The mixing ratio of the first metal to the second metal is 001:10 to 1:01; For example ; SY) 1:54 - 6:61 DNA from 09:1 to 0:19 or from 1:01 to A Catalysts may also include selected Group III metals from any of the metals mentioned above in VO contact with the first or second metals; As long as the third metal differs from the first and second minerals. It is preferable that the third metals be determined from a group consisting of: Laie cobalt, palladium, ruthenium, copper, zine, platinum, tin, and rhenium so that there is a gradient in the catalyst. It is preferable that the third metal be present in proportions such as 0005 7 or Lg ; or even 0-0 for (or) = IY of the total weight.

DC - additionally one or more minerals may form; catalyst for any Agee modification; This includes mass support and a support modifier that adjusts the acidity of the mass support and total weight; Based on the total weight of the catalyst or preferably from VO = 4969 7 to reach the ideal weight; and for example ; 0 Sel 47 - 1 VA - 40 7. It is preferable that the material used to support the modification is (©) with a percentage of (ve) weight 78 lege for example + from a = yo from q - ram or from ‎ A - 1 gross weight; And based on the total weight of the catalyst. A suitable distribution may be obtained for materials including; Acid or alkaline stable minerals. ; Such as silica / alumina; and the group of calcium metasilicate Jie ¢ and silica alge for fever; and high purity silica; and mix them. Other materials may include; But Clade Ve is not limited to iron oxide, alumina, titania, zirconia, magnesium oxide, carbon, graphite »and carbon; carbonate in general. and as indicated above; The catalyst is modified with the mass rate; Which is the rate of the underlying material having low volatility or no volatility. ; For example ; The modified material is not removed due to fluctuations or chromatographic effects. And so on ; The modification does not require on-site replacement. such as 0 basic adjectives; They may be chosen from a group consisting of: (the first) alkaline earth oxides (the second) alkali metal oxides (the third) alkaline earth metals (the fourth) metasilicates alkali metals; (v) group metal oxides; (vi) metasilicates of the group of free metals; (vii) Metal 118 group oxides; (eighth) metal 118 metasilicates; and mix them. In addition to oxides and 9 other types of minerals, including nitrates, nitrites, acetates » and each of them is sorted separately to be

— $ \ _— use it. It is preferable to specify minerals from a group consisting of oxides and of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc ¢ as well as a mixture of any of the above (03S), preferably calcium silicate sa ¢ more than .CaSiO3 calcium if the modification includes calcium; Preferably, it should not be less than a part of the sandalah »in crystalline form. © and the bulk support is silica preferably silica as a catalyst 0 Jib and the silica present is about de 7 by weight so that the average pore diameter is about 11 nm; The average pore size is about 0.1 mm / gram measured by porosimetry, and the scattering density is about (YY) aba / jo YoY - (Ib / f3). It is preferable when using alumina / silica in the silica bulk support. with a nominal diameter of about 01 mm, a density of about 7 g/l' in |, an absorbance of z/HO of about z / + OAY, and an area of about yo' — 0 g. / mm Y, and a pore size of about “A ml | c.” The materials of this mixture are selected so that they are suitably active catalysts, pure, and strong under the practical conditions used to form ethanol. Yo and metals are catalysts. They may be throughout the shell encapsulated on the outside (egg shell) or present on the surface.These catalyst compositions are suitable for use with this invention and are preferably formed by mineral impregnation of the material;and also from other processes such as vapor deposition of the chemicals used.They have been

- 1 and

These technologies are described in US Patent No. 7581/44 + 4/84 1437 f” published under No. 47400 (forerunner LEY). In some reactions an innovative process uses configurations using a fixed reactor and/or fluidized reactor; as one of the interactions. In applying this invention; A cull reactor can use heat so that there is little or no need for internal energy through the reaction zone or to

Add or remove heat. A radial flow reactor may be used or a series of reactors may be used with outside heat exchange; cooling; or enter additional materials. Alternatively a shell and tube elie may be used with medium heat. in many cases; The reaction may take place in a single process or in a series of processes with therebetween heat exchangers.

0 preferred interaction; is the work of the catalyst in a stationary reactor; For example ; in the form of a tube; Where the substances involved in the reaction are passed; usually in the form of steam; And through more than one catalyst. Other reactors may be used; such as lukewarm fluid reactors. in some cases ; Hydrogenated catalysts may be used in conjunction with inert ale to regulate the pressure drop of the reactants stream during the contact time between the reactant compounds and the catalyst particles.

1O The hydrogenation reaction may take place in either the liquid phase or the vapor phase. The reaction should preferably be carried out in the vapor phase under the following conditions. so that the temperature ranges from 15 degrees Celsius to You degrees Celsius; For example ; From Yor degree Lda to YYO degree ; and from YYO the degree of Liste to 701 degrees Celsius; Or You °C to Too °ge when it passes an acetaldehyde feed comprising ethanol acetaldehyde ¢ The reaction temperature may range from 111

Ye is a degree to 100 degrees Celsius; For example ; From 151 degrees Celsius to 775 degrees

- 11- Up to 7000 kilometres, 01 degrees Celsius to +15 degrees Celsius. And the pressure is from 175 BP or 001; from 00 = 7300 or from JU up to £0 lbs); For example Veo Pa (approximately (GHSV) kPa. The reactants in the reactor may have a gas velocity per hour Vo + 0 [Your / hour; and greater than 10001 h; ie; more than / 1 0 greater than 1 - 50005 GHSV hours between 1 - 50005 hours or even more than 5 / hour in terms of 00001 - 0001 - 0001 hours to 0000© / hour from / 1 ovr for example; from .aes/0001 to 1 or from

GHSV and hydrogenation are carried out at only enough pressure to overcome the pressure drop across the catalyst at the specified ¢ although there is no table for the use of pressures above; It being understood that a greatly reduced [oe] pressure drunk through the reactor may lead to high velocities; For example 0 hr or 18086/hr.” acetaldehyde acetic acid in mol of hydrogen The reaction consumes two molecules of acetaldehyde in a feed stream may play to mol of hydrogen; and the ratio of ethanol to yield_ One mole of reaction in the reaction (0:08 to Are) or 1:01 to 001:00 ranges from 70:01; For example; range between 70:01; for example acetic acid to one hydrogen; The molar ratio may be the ratio of _5 to hydrogen up to 1:08. in one interaction; and the ratio of Ane) or 1:01 to 1:00, for example; and at the end, Ane) 4:01, for example; or greater than YoY greater than acetaldehyde mol greater than 1:; For example ; greater than the molarity of acetic acid of hydrogen ; Jeli nose cg

11- These ratios can also be used extensively; Depending on variables such as the amount of acetic acid ¢ catalyst; temperature reactor; and pressure. Typical reactions range from a fraction of a second to over several hours when using a catalytic system compared to using a stationary system; at least for vapor phase reactions from ve) to 100 s ; For example ; 1” 0 to 81 sec or eet to AY may be using oil derivatives and raw materials of hydrogen and optionally 8610 acetic and/or ethanol; and used in the process of this invention from any suitable source including natural gas, petroleum, coal, and biomass; and so on etc. And if acetic acid is present in the feed stream; It may be produced via the carbonization of methanol “and the oxidation of acetaldehyde ¢ 0 oxidation of ethylene; fermentation; oxidation; and anaerobic fermentation. And the carbonization of methanol is a suitable process for the production of acetic acid in US Patent No. 186 VYIYOVVY ¢ mma. ; e and previously referred to 0 in one of the interactions; When ethanol is present in the feed stream; Ethanol may be obtained from 0 ethanol mixture produced by hydrogenation of acetaldehyde . and if acetaldehyde is present; and evaporation of acetic acid) and | or ethanol in a vaporizer; to the reaction temperature; It is introduced into the hydrogenated Jeli. The acetaldehyde feed stream works to evaporate it and then put it with undiluted hydrogen and it can be added with a carrier of relatively inert gas such as nitrogen, argon, helium, carbon dioxide and the like. During operation of the 0 steam stage, the temperature in the Jie should be controlled in such a way that the dew point does not fall from

-\A- at a given boiling point and pressure; Then the acetaldehyde is heated and the acetaldehyde is evaporated into acetaldehyde and evaporated and put into the thermal reactor. In the last reaction, Bakrg 618106306 is transported by passing hydrogen vapor; gas recycling “so that suitable gas is used; at a temperature lower than the boiling point of acetaldehyde or mixtures of gases through; followed by acetaldehyde and appropriate humidity; via carrier gas with ¢acetaldehyde© vapors Heating with mixed vapors reaches reactor temperature. acetic acid and ¢acetaldehyde evaporates; In addition to acetic acid, it includes acetaldehyde and feeds the evaporated into acetic acid at a certain pressure ¢ and then heating the acetic acid molecules at a boiling point to the barrel by passing hydrogen vapor; acetic acid JB temperature reactor. And ¢ acetic acid is heated below the boiling point of dap in acetic acid and the gas is recycled through Ve followed by heating mixed vapors up to a temperature of ¢ acetic acid using carrier gas with vapors, the best ethanol and/or acetic acid and if “acetaldehyde” is the reactor. Preferably acetaldehyde and/or gas recycling via hydrogen is converted to steam by passing a centigrade; followed by heating 1*5 in temperature or less ethanol and/or acetic acid + the combined gas streams to the reactor temperature. Vo ¢ (if present) acetic acid; In addition to hydrogenation using acetaldehyde, selective hydrogenation is preferred to complete the process. Je acetic acid; and optionally acetaldehyde by the method of conversion from indicates the amount of the “unl” yielding component of ethanol. For the purposes of this invention, the term “in petroleum derivatives for which acetic acids ¢ acetaldehyde is specified,” for example; or acetaldehyde to be converted to another compound.The conversion is as an eligibility ratio based on the amount of Yo

- 1 -

acetic acid (whichever is specified) in petroleum derivatives. Preferably conversion of at least Vo 7 ; For example ; A minimum of at least 85 0 FL 7. If acetic acid is present in the oil derivatives; and perhaps the conversion of La acetic acid is not less than 7 01 ; For example; not less than Le 7 00 not less than elon cl tr least ; at least 60 7 I've © at least ; or at least LA despite the stimuli that motivate conversions to rise; A minimum of at least 0 SLA 7 + acetaldehyde and/or acetic acid (if present) and low conversion is acceptable when there is high ethanol selectivity. It is within the scope of the invention to compensate for the conversion decrease by using appropriate basket streams or larger reactors.

may be however; More difficult to compensate for selectivity.

0 and the purity is in percent based on the mass of the converted reactant; When using acetaldehyde / or acetic acid. For example ; If 70 7 of acetaldehyde is converted to ethanol ¢ it is indicated that the selectivity is 0 7 01 ethanol and the selectivity in acetaldehyde and | or acetic acid ethanol not less than 80 7; For example, Loe is not less than LAL blood rar a0 at least. The selectivity of acetaldehyde to ethanol is higher than that of acetic acid.

0 to ethanol ¢ for example; no less than 7 01 ; not less than 75 7; or a minimum of 8.1 00 preferred case; The selective hydrogenation process also has a decrease in unwanted products; Jie is methane gas and sap.” and carbon dioxide. and selectivity for these unwanted products is preferably of 4 7 ; For example Jl is less than 1X or less than . 1 These unwanted products are not easily detected in the product. in one of the

7 7 Low. For example ; One side in less than alkanes may interact and form 0

a. is less than or equal to 71 leo of acetaldehyde | or 1 806068 passed over a catalyst that can be converted into alkanes of little value other than as fuel. the term I for productivity ' as used in this invention; It indicates the number of grams of a particular product eg; ethanol; It was formed during hydrogenation on the basis of kg of catalyst material © used per hour. Yields of at least yo grams of ethanol per kilogram catalyst per hour are preferred; or not less than 400 or not less than 00010 ; The productivity is preferably from 0.001 to 0 g of ethanol in a catalyst, kg per hour; For example ; from 4060 to 70060 or from 010 to 00000 in a different interaction; the raw product will be from the effluent; and for example ; ethanol mixture; before any further processing; Such as 1 water purification and separation; It includes ethanol sale, water and small amounts of (unreacted) acetals “ethyl acetate ¢ acetaldehyde” and acetone; and optionally ye) the reactant is acetic acid. An ideal inclusion of the synthetic ethanol AAN ranges is provided in Table 1. It should be understood that the 3 ethanol mixture contains other ingredients that are not listed. Table 10 mixtures of ethanol d

071 - - Quantities indicated in less than (<) in tables in all values of the current table and preferably not present; But if they exist; May be present in trace amounts or in larger amounts (Jove) in a single reaction ¢ The 08001 mixture may be purified in one or more distillation columns to remove impurities. © Described by suitable purification systems as contained in Patent No. Rafaa Alaf 4 + and 87/17 » 797; It has already been referred to. This invention provides a raw ethanol mixture that contains smaller quantities than other products. For example ; ethyl acetate. And so on ; The resources required to separate these other products from ethanol are reduced. Vo the purpose of tables 1 and ? Demonstration of the hydrogenation system 001 suitable for the hydrogenation of acetaldehyde acetic acids » hydrogenation of acetaldehyde optionally ¢ and separation from ye ethanol of the crude reaction mixture according to one of the applications of the invention. System 011 includes 0101 reaction area and distillation area. F Reaction area 011 includes 017 as reactor; and hydrogen feed line 0304 Yeo acetaldehyde feed line; Optional Feed Acetic Acid; Veo Line; And optional 011 ethanol feed line 0 ". It is preferable to have a V + © acetaldehyde feed line from the material flowing by the producer for the vinyl acetate production process.

in fig. 1; 011 distillation area includes 011 ; first column 0107 ; 018 second column; And the third column is .0014 in the figure. 7; 017 distillation area also includes a fourth IVY column and hydrogen is fed acetaldehyde s », acetic acid and / or ethanol; To 011 atomizer via lines 015 Veo hed and 10" respectively; to create steam feed stream in line ANY© line 111 is routed to #01 reactor. and lines 014 and 015 They may be combined together as they are transferred to the vaporizer 0011, for example JU, in one stream containing both hydrogen and acetaldehyde.The temperature of the vapor in the feed stream of line 111 is preferably of 001 degrees centigrade. to yor °C 101 °C to 01 °C or 0 °C to 00 °C Any non-evaporated material is removed from vaporizer 001 as shown 0 in 1 and ?; shall be thus recycled. In addition; although 1 and 7 line 111 is directed to the top 0007 Jolie line 111 may be directed to the side; and the top or bottom of The Vo reactor is described with further modifications and additional components to the area

Interaction 011 below. 0” reactor containing the catalyst that is used in the hydrogenation of acetaldehyde as the catalyst is used in the hydrogenation of Vo ¢ carboxylic acid and 1 ure acetic acids. In one reaction, one or more reactants may be used (not shown ) to protect the catalyst from toxins or undesirable impurities contained in the feed stream or return or recycle streams. These reactions may be used in vapor or liquid streams. Suitable materials are known to include; for example ceramic, carbon, and silica ¢ aluminas + or resins and the raw ethanol product is drawn continuously 017 Jolie ge 0 through line 117. la ethanol product may be condensed and fed into 011 which in turn provides a steam stream and liquid flow.When Vo works preferably at a temperature of Celsius

from 560 to ony degrees psa; For example ; From 1°C to tee is a dew degree or a dew degree from 001 to You is a dew degree. 011 pressure preferably from 0.56 - 0...; For example ; 5 = 1501 kPa or 001 to 0001 kPa. It is preferable that the temperature and pressure be similar to the temperature and pressure of the AY reactor © from which the steam stream comes out, and here 7 may include hydrogen and hydrocarbons; Ally can be removed and/or returned to the interaction area via the 011 IY line and as shown in Figures 1 and A; And return part of the steam stream that passes through the compressor 114 and along with the hydrogen feed stream and participates in feeding the co-fed to vaporizer + 1) the liquid is withdrawn and pumped to 11 as it is responsible for the formation of oil derivatives through a line 0 1119 next to first column 011 ; The acid is also referred to as a separation medium. The contents of the VY 0 line will be sold very similar to the products obtained directly from the reactor; It can be described as a 2h ethanol product however; the composition of the derivatives (hil) in the 119 line preferably a large amount of 4s ¢hydrogen carbon dioxide ethane s methane. or that is removed by LY oT and YO presents the ideal liquid components in the line Yes as Table 7. It should be understood that the liquid line may contain other ingredients » not listed. Table Y ET TE

we didn't insist

Ss values indicated in less than (<) in tables throughout the current request are preferably other than 00001 present; But if they exist; It may be present in trace amounts or in larger amounts

J: Table 7; Such as, but not limited to, 8" esters' © or ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate diethyl ether, ¢ other ' in table ¥ but are not limited to ethers' mixtures thereof. Others' in table ¥ includes alcohol' mixtures thereof. and methyl ethyl ether, isobutyl ethyl ether or methanol, isopropanol, n-propanol, n-butanol ¢; But it is not limited to exclusive mixtures of them. In one context and composition of petroleum derivatives; For example ¢ 110; It may include 0 ¢ by weight of 1-000 by ¢ isopropanol and/or n-propanol + eg ¢ propanol and it must be understood that these components can be implemented 1 0 (m1 or t). Other F through any of the distillate or residue streams described here ¢ and will not be described unless otherwise indicated. Lae here

vo - - in the following part where the ethanol feed includes 5 acetaldehyde and the crude reaction product and preferably includes less than less than © in the weight of 7 acetic acid under these conditions; The acid in the separation tube 011 may be skipped and the 10 line can be inserted directly into the second tube BLY A The second tube is referred to here as 018 "The light ends here." It includes an acetic acid acetaldehyde© feed stream that undergoes a high conversion process; The acid in 011 may be skipped. in these cases; To the liquid in line 111 so that it is less than S807 the weight of Seo dL for example; less than JV in this part as shown in the figure. 1 is the width of the 111 line at the bottom of the first column 011 ; For example ; Less than half or a third less. in the preferred interaction; 0 first column 01 may be used to remove unreacted acetic acid to feed reactor .017 in these cases; And the nutrition includes acetaldehyde and its acetic. in the first column 011 ; unreacted acetic acid ¢ and part of the water; and other heavy components 0 are removed from the formation in the Yio line and withdrawn; Preferably continuously. Some of the WED JS may be returned and/or recycled back to the reaction region via the 011 MYT line although it appears as a product residue with in-acetaldehyde Vo as in Figs. 1 and ? ; The residue is sent directly through the AVN atomizer line. The first 011 column also forms the distillate; drawn in line 117 which might be REC + for example; In a ratio of 001:00 to 00:1; for example 3:00 to 0:07 or 7 -1:0. Any of the columns 177 » 008 + 008 + 007 or the distillation column may be capable of separation and/or purification. The columns form Vo - 1 - and for example Che - 0 J 0 48-700 or © = VO . The valves may be either a fixed valve; or a movable valve; Or any other suitable design known in laboratories. in other applications; The work of an organizer may be packing or

A - random packaging. The arrangement of valves or packing may be continuous in one column or it may be arranged in two or more columns so that the vapor from the first section enters into the second section while the liquid from the second section enters into the first section; etc. The condensers associated with separating liquids that can be used with both distillation columns may be of either conventional design or simplified in shape. .1 © as shown in the figure. 1; The heat is supplied to the base of each column or downstream of the circulating stream through a heat exchanger or "alternator". Other types of reboilers can also be such as internal reboilers ¢ The heat supplied to the reboilers can be derived from either the yall generated during a process that the reboilers are integrated with or from an external source such as another chemical process generating thermostat or boiler. 1 can be used; additional reactors; capacitors; heating elements; and other Ve elements in the embodiment of this invention. It will also be explained by that skill in the various capacitors, pumps and compressors Reboilers 0 » ¢ ; valves; which are normally employed in carrying out chemical processes and may be combined with those employed in the processes of the present invention. The temperatures and pressures used in any of the columns may vary. from scientifict side ; In general, pressures from Fore = 10 kilopascals can be employed in these areas, although in some cases it is permissible to use subatmospheric pressures as well as -superatmospheric pressures and temperatures in different regions ranging from sale between the boiling point. such as the removal of distillates and the formation and removal of residues. It will be explained that the temperature at a particular place in the operating distillation column depends on the material composition at that location and the pressure from the column. In addition ; Feed rates may vary depending on the scale of the production process; and if it can be described; Can 0 - is generally referred to in terms of the weight ratios of the petroleum derivatives.

Except - when 110 columns are operated under normal atmospheric pressure; The temperature of the exit at the 111 residue line of the column is 0.11 °C preferably from 40 to 181 °C; for example JU; From 011°C to 117°C or 011° from Agia to 111° C. And the temperature of distillate output in column 111 of 0117 columns preferably from 0ºC to 011º Aggie, for example; From Ve degrees Celsius to Lape Asie or Augie degrees from Av to 0 degrees Celsius. in another experiment; The pressure of the first column 011 may be 1 ; For example ; From EVO - 1 kPa or from ¥Vo -1 kPa. The exemplary components of the distillate and residue formulation for Column 7110 are provided in the table below. It should also be understood that distillates and sediments may also contain Ve other components; not listed; such as ingredients in petroleum derivatives. for convenience of work; The distillate and first column sediment may also be referred to as 'first distillate' or 'first residue'. The distillates or other columnar residues may also be numerically indicated with italics (second, third, etc.) so as to distinguish them from one another; But these rates should not be construed to require any special chapter order. 0 schedule? The first column is a fe [te [te] es

YA - - ِ pw as shown in the table; It was discovered that when any amount of acetal was detected in the feed that was introduced to the acid column (first column, acetal Jaen ) for decomposition in the column, so that it became less even when any quantities were detected in the distillate and/or sediment. Depending on reaction conditions ¢ the raw product ethanol may be in the reactor exiting 111 (ANY) in a step including acetaldehyde ¢ ethanol (unconverted) ¢ ethyl acetate and optionally acetic water (unconverted). exit from 017 into a reactor; non-catalysts may react between components in the raw ethanol product until it is added to 011 and/or first column LY eV this equilibrium tends to push the pladl ethanol product into equilibrium between Acid [ethanol] vinegar [ethyl acetate] water and distillate, for example, the convection current of the column is 011 Yo are condensed gases, as shown in Figure 1, and it is preferable that The ratio is from 1:06 - .0060 and the distillate in the 1117 line preferably includes ethyl acetate “ethanol ¢ and water; along with other impurities; which may be difficult to separate due to the formation of 08. Here Display of distillate in the first line 111 to the second column Veh preferably in the middle part of the column Vo A; when the YO column is used without water extraction; in

_Yq—_

one of the applications; The second column may be a Vo A column of extractive distillation. in applications such as

This is amazing ; extraction agent may be added; like water; And the second column is .008 if it's the extraction factor

featuring water; It may be obtained from an external source or from an internal return from one or more lines

from other columns. In the second column 018 the column is part of the reaction in different proportions. and on

40 - 71 fou - 10 Jul Sabeel ©

Although the temperature and pressure of the second column 0118 may vary; at atmospheric pressure

At a certain temperature, the residue of the second comes out of the second column, 0118, preferably of 01 degrees

gestational to 0° gestational; For example ; Vey is a degree Celsius or 0 degrees

Gynecology from A to 90° Gynecology. The temperature of the secondary distillate exiting the second column is #00#01 preferably from 00°C to 0°C; From Te degrees Celsius to A

Feminine degree or Feminine degree + to Ye is Feminine degree. It may operate at atmospheric pressure

Column #01.In other applications; Compression from the second column oY ae 0 may be hot on

example from 1 - 75; kPa or from 1-375 kPa.

Ideal ingredients for the composition of distillates and residues are provided for the second column in the table; below. 0 It should be understood that distillates and sediments may also contain other ingredients; not listed; like

components in petroleum derivatives.

schedule ; :

second column

ahn set | Intersected || unless

kh ala ae) Yeu +1 <V ethyl acetate — ° f 0 acetic acid m > | lrresem) 0 — oY The weight ratio of ethanol in the second residue to ethanol in the second distillate is best at least:1; For example ; no less than 6:00; Are) at least; not less than 10 011 or at least: .1 weight ratio of 8061816 ethyl in second residue [ethyl acetate] in second distillate preferably less than 4:1; For example ; Less than 1,1: Yn) or less ©. in stages using water as extraction agent and second column 018 ; The weight ratio of ethyl acetate in the second residue of ethyl acetate in the second distillate approach is zero. And as indicated; and the second residue from the bottom of the second column 018 ; which includes ethanol and water; It is fed by line 118 to column 01 ACB ; Also referred to as 'product column.' The second residue in is the width of a line of 118 at the bottom of the third column, eg Ved Ve; the lower half or lower third. The third column, ethanol, recovers 004. It is preferably pure with a large degree of water content that resists boiling, as distillate in line .119 in the third column of distillate 014. It is preferable to be as shown in Figure 11, for example, in a ratio From Tefn Hajnet Sadah Nar Ten 01-7

_y\_

the third residue in line 111 ; Which preferably comprises primarily water ¢ preferably removed from system 0 or may be partially returned to any gia of system .001 3rd column is preferably 4 column as shown above ¢ preferably at atmospheric pressure 0 That the temperature of the third distillate in line 119 of the third and best column is from 015 00 °C 01 to 011 °C ; For example ; From °C Ve to 001 °C or °C from VO up to 46 °Augie temperature the third residue exits from the third column is best from 0019 °C Ve to 108 °C cpa for example; From Av degree to 110 ° C or from Ao degree to 01 degree C ' and when the column is operated at atmospheric pressure. The typical components of the formulation are distillates and residue 01 third column are given in Table 0© below. It should be understood that the distillate and sediment may also contain other components;

not listed; such as ingredients in petroleum derivatives.

Table © a third column next to || ed 1 acetic acid > 1p - 0 1 aa ethanol > 61 0 5 a

ace -

1 ethyl acetate 1 p salt

A L A

acetic acid 1b 61 - a

a 7 any of the compounds that are made through the process of distillation from raw materials produced generally remain in the third distillate in weight less than the amounts ve) 7; On the basis of the total weight of the composition of the third distillate; For example ; Less than 700005 wt or less than 7 wt. In one of the reactions one or more side currents may remove impurities from any of the AY columns

AY uses and preferably at least one side stream .001 in order 1" / or 01018 eo

Impurities from the third column Ved The impurities can be removed and/or retained within the 001 system. The distillate in the third line may need further purification to form a waterstream ethanol product + i.e. finished with e SLU ethanol using one or more additional separation systems 1 such as distillation columns or molecular sieves.

0 and back to the second column 0107; The second distillate is preferably as shown in fig. 1; For example ; in a ratio of 1:1 to 10:01 1:05 to 0:00 or 0:7 to 0:00 (BLT Fig. 1); the second distillate may be removed or recycled back into Reaction area .011 in Fig. 7; feeds second distillate through line 171 to 177 fourth column; also indicated as “Column 00021080908E Removal.”; in fourth column 1173 may be used

Lorie Yo the amount of acetaldehyde is large ¢ unreacted acetaldehyde sf or produced from the hydrogenation of sour vinegar ¢ its proportion is greater than 11 by weight; and for example ; bigger ? Weight or more than 75.

name_ and in the fourth column YY ; The second distillate is separated into the fourth distillate in a line; which contain acetaldehyde; and fourth residue in line 1*6 ; containing ethyl acetate. The fourth distillate is preferably reverted in the reflux ratio from 0:01 to 70:01; For example ; Vivo until 15:00 or 0 to 00:01; eda is returned from the fourth distillate in zone 10010 in .10010 and part of the fourth distillate is removed. For example ; The fourth distillate may be combined with acetic acid, if present; In addition to the 011 vaporizer; Or add it directly to the 011 0 reactor in one embodiment and the fourth distillate is acetaldehyde in the 0 feed line to the 011 vaporizer. And the fourth distillate with acetic acid may be feed line 011 "if present; or feed ethanol into line 010."

Ns 0 This invention hydrogenates acetaldehyde to form ethanol ¢ Recycled to the stream containing acetaldehyde; For example ; Stream 4 + The use of ethanol affects the increase or decrease of the product and the generation of waste. In the last reaction (not shown) Acetaldehyde may be collected and used; with or without further purification; to make useful products including but not limited to 1 n-butanol, 1,3-butanediol and | or crotonaldehyde and its derivatives.

The fourth ethyl residue comprises mainly 5.) Y0 via line 171 and the fourth residue can be removed from the fourth column 0 which may be suitable for use as a solvent mixture or in the production of 5 ¢ ethanol acetate from the second distillate In the column are acetaldehyde esters. In one preferred embodiment » 117 is removed so that the 6 contained in the remains of the 117 column cannot be detected. The fourth column is preferably as described above; Preferably, it should be 177. The fourth column is

00 is higher than atmospheric pressure. Fourth column pressure preferably VY from 000-170; on

Y 4 — _ Ex. 001 - .mph or from -55668 Fave kPa. In the preferred reaction the fourth column 1” may exert a higher pressure than the other columns. The temperature at which the fourth distillate exits in line 174 of the fourth column is preferably from 61 °C to 110 °C » for example from 001 °C - Vo °C or a residual °C of Vo - 0 © degree of residuality. The temperature at which the residue comes out of the fourth column is preferably 111 °C or 01 to 111 °C; Or from Av °C to 011 °C or from AO °C = 10101 °C. The ideal components of the formulation, distillate and residue of fourth column 01" are in table 1 below. It should be understood that distillate and sediment may also contain other components; they are not listed; such as ingredients in feed. Ve table +

The fourth column

tw] dw] a]

Lls

Tw

>11 Acetaldehyde 61 not detected

0 o

Lay - ethanol mixtures produced from this invention can be used in a variety of applications including fuels, solvents, chemical raw materials, and pharmaceutical products; & ¢ Disinfectants &Disinfectants; and in fuel applications; And mixtures of ethanol are mixed with gasoline for cars, boats and small-engine aircraft. in non-fuel applications; © ethanol mixture may be used as a solvent for the preparation of toiletry, cosmetics, detergents, disinfectants, coatings, inks, and pharmaceuticals. Lind can ethanol mixtures be used to prepare solvents in manufacturing processes for medical products and food preparations; Dyes, processing photochemicals, latex, and ethanol mixtures Lind can be used as a chemical intermediate to make other chemicals such as ethyl acetate; ethylamines glycol ethers ethylene ethyl acetate aldehydes and high alcohol, especially butanol. In the production of ethyl acetate ¢ has accumulated in mixtures of ethanol with acetic acid or reaction with polyvinyl acetate. It may be desiccant and ethanol mixture to produce ethylene. Any of the known dehydration catalysts can be used to dehydrate the ethanol; Such as those described by 0 in Patent No. aT Y/Y OY 1/1818 - and a zeolite catalyst may work; A special action ole ly dehydration catalyst. The zeolite has a pore diameter of at least ved nanometers.” Zeolite catalysts include a selection of mordenites “2834-5” and are contained in patents No. 1887744 and No. 7070011; It has already been referred to.

The invention is described in detail below with several applications indicated for illustrative purposes only. Modifications ala will be made within the spirit and scope of this invention ¢ set forth in the claims. The following are examples describing the procedures used to prepare the various catalysts used in this invention. © Examples: Example 1 feed stream of acetaldehyde comprising 0 © / by weight of acetaldehyde + and by weight of +© / of hydrogenated acetic acid in the presence of a catalyst including ARTE by weight of Css platinum 7 Tin 0 based on A / 1 inch calcium silicate modified silica extrudates The hydrogenation reaction was carried out in the vapor phase at You temperature Agia degrees ; And your pressure is psi and at 717 from 4080 - 1 h. The composition of the raw ethanol mixture in the waste effluent reactor is given in Table 7 below. Example 1 Vo is hydrogenated acetaldehyde as in Example 1 ; But at a temperature of 700 Aggie degrees the composition of the raw pile ethanol mixture in the effluent reactor is given in Table 7. Example?

The acetaldehyde feed stream after / 0 wt. Effluent reactor in Table 7. Example © feed oxen acetaldehyde hydrogenation as in example ? ; But at 701 degrees Celsius. The composition of the raw all ethanol mixture in the effluent reactor is given in Table 7. Table 17 Te aw [Te IEE I eo | or | 0 | 0 | Masam Aha || Ce ew |e 00 degrees 0? 0 degrees 0 degrees 0 degrees HS [saws] | ed ae ve ee

To [ee Je | ath prem ld =| Co mmo | oa a acetaldehyde thaler acetic acid Examples 1 and ? ; The yield was greater than ethanol at high temperature. The acetaldehyde ethanol feed stream examples of “and ;” have a greater yield than |ethanol at a lower temperature. Conversion of acetaldehyde to ethanol is a lower heat output and reaction temperatures are more beneficial. It is believed that the conversion of ethanol to acetic acid to involve at least two of the steps.The first step is to convert acetaldehyde acetic acid which is endothermic.The second step is to convert acetaldehyde to ethanol and the first step is slower than the second step.Also the The first step also yields water as a co-product.In each of the examples, the conversion of acetaldehyde to ethanol greater than 96 J for the examples ©and a feed stream started with an ethanol weight of 0.0/.It is believed that this ethanol 0 and proceed through the reaction essentially unchanged during hydrogenation.While the invention has been described in detail ¢ and modifications within the spirit and scope of the invention shall be apparent to those of skill in the art.In light of the foregoing discussion ¢ and relevant knowledge in the art and references made Discussed above in connection with background and detailed description; and disclosures which are all incorporated herein by reference. In addition; it should be understood that aspects of the invention and parts of the different application and different features as presented below and/or in the claims appended may be combined or interchanged either

and LS or part. In describing the above from a different application; The application of those referring to AT may be applied appropriately combined with other inclusions that would be appreciated by one of the skill in the art. Furthermore ; For those of ordinary skill in the art appreciate that the foregoing is described as an example only; It is not intended to apply an invention. °

Claims (1)

Protection Elements 1-1 A process for producing an ethanol mixture that includes hydrogenating an acetaldehyde feed (so stream Y) with a catalyst to form the ethanol JEN! mixture; So that it includes an acetaldehyde stream ¢ and a reactant selected from the group containing acetic acid ¢ and ethanol, and so that the first catalyst includes metals, a silicaceous support and a support modifier © 1?- dle of claim 0 so that it feeds a feed stream of Cus acetaldehyde Y having a value of 775 to 72490 by weight; and a reactant chosen from the group including acetic acid and ethanol and having a value by weight 01 7 to JVe 1 ?- A process according to protection elements 1 and ¥ which contains a feed stream of acetaldehyde comprising from 701 weight to 175 weight of aceticacid. 1 4- A process in accordance with the elements of protection from 1 to ¥ which contains a feed stream of acetaldehyde ¥ comprising from 7201 weight to 71759 weight of ethanol Adee - # 1 According to protection elements from 1 to 4, it consists of: vaporizing a vaporizing feed stream Y of acetaldehyde to form a vapor feed stream; And activating the reacting the vapor feed stream in the presence of the catalyst And 1-1 process according to claims 1 to © ; Where the hydrogenation is carried out at a temperature of ¥ from 11 ° C to You ° C. 1-17 1 Gig process for safeguards from 1 to 6 ¢ where hydrogenation is carried out at a pressure of 01 to 000 kPa. 1 + - a process according to protections from 1 to oF so that the hydrogenation is carried out with a Y molar ratio of hydrogen to acetaldehyde from 1: 01 to .01: 1 1 9 - A process according to the protection elements 1 to Cus A. The conversion is from 8064010603708. In the V feed stream of acetaldehyde from 7709 to 7001 and conversion of acetic acid. In feeding the acetaldehyde stream ¥ from 01 / to J 001 ethanol mixture to 46, where the ethanol mixture includes 1 process according to the protection elements of 1-01 on the following: X. ethanol by weight of 7 AY ML 0 of YF ; From vay 2 to yo 7 by weight of water. 8 from 0.001 to Yo 7 wt of aceticacid ; and 1 from 0.2001 to 7 01 7 by weight is acetaldehyde . lee -11 1 according to Claims 1 to 01 ; It includes the purification of the ethanol mixture in ¥ separation units to produce ethanol. -11 1 operation according to claims 1 to 11 ; As the first metal is present in the amount of 0 to Lye of weight; And based on the total weight of the catalyst and selected from the group that consists ¢ palladium rhodium ¢ ruthenium y nickel sy cobalt copper and iron ¥ *; rhenium chromium zincy ¢ titanium platinum iridium + osmium; tungsten + molybdenum © . ‎Adee-1? 1 according to claims 1 to 1; Where there is one booster for the enhancer in the amount from 700 yen to Joo by weight; And based on the total weight of the catalyst selected from a group consisting of (1) pals] ¥ alkaline earth metal oxides (Y) alkaline earth metal oxides 1 alkali metal oxides ¢ (¥) metal alkaline earth metal “(¢) alkali metals” (5) 0 metal oxides metal oxides group IIB ¢ (1) metal of group (V) ¢” IIB group metal oxides MB; (A) MB ¢ group minerals and mixtures thereof. 19; Where the reinforcement is present in the quantity from 775 to 11 to 1 process according to the protective elements of 1 - 1 silica « silica by weight; And based on the total weight of the catalyst selected from a group consisting of XY and a mixture thereof. -1#1 process according to claims 1 to 14 ; Where the catalyst includes a second metal different from the "first metal", so that the second metal is available in the quantity from 07 - 700 by weight; and based on ' _ the total weight of the catalyst chosen from a group consisting of 1 molybdenum + copper alloy; and chromium ¢ tin tin, iron, palladium 5 tungsten s vanadium – cobalts iron – rhenium – ruthenium – manganese – cerium – lanthanum – platinum©, and gold 5 .nickel: A - 11-1 Process for producing an ethanol mixture (Jl) “¢ which includes: contacting a mixture of ethylene and vinyl acetate zy oxygen ae acetic acid and the current product comprising acetaldehyde ; and Y hydrogenation of at least ga of current by at least one product in the presence of the catalyst to form a mixture; ethanol mixture. -17-1 process pursuant to claim 06; So that the flow by the producer is at least one and includes Y from 50 to 7954564 by weight acetaldehyde . VA) process according to protections VT and VY; Comprising vaporization of a product stream (gol and a reactant selected from the “group containing ethanol acetic acid”; to form an olay feed stream and a recovery of the Y vapor feed stream in the presence of the catalyst. V8) process according to component protection VA¢ in which there is a steam feed stream comprising from 15 7 to 40 1" by weight of acetaldehyde; And from 701 to 77/5 of the weight and the chosen reactant of the group containing ethanol 5 aceticacid 0 . -71-1 process according to claims 11 to YA; The catalyst includes a mixture of selected metals from Y group consisting of [platinum tin platinum ¢ ruthenium / platinum ¢ tin palladium | cobalt ¢ rhenium / palladium ¢ ruthenium / palladium ¢ rhenium ¢ ruthenium / cobalt [ chromium cobalt | platinum | cobalt ¢ ¢ silver palladium © ¢ palladium contact | nickel ¢ palladium / copper ¢ gold / palladium ¢ ruthenium 3 ¢ rhenium / ruthenium 1 [ iron .