WO2013029129A1

WO2013029129A1 - Integrated system for producing ethyl acetate, acetaldehyde, hydrogen and ethylene, integrated process for producing ethyl acetate, acetaldehyde, hydrogen and ethylene, and products thereby produced

Info

Publication number: WO2013029129A1
Application number: PCT/BR2011/000458
Authority: WO
Inventors: Rubens Maciel FILHO; Maria Cristina de ARAÚJO
Original assignee: Universidade Estadual De Campinas - Unicamp
Priority date: 2011-08-31
Filing date: 2011-12-07
Publication date: 2013-03-07
Also published as: BRPI1104013B1; BRPI1104013A2

Abstract

The present invention describes an integrated system for producing ethyl acetate, acetaldehyde, hydrogen and ethylene with high added value, by means of a process including a reaction step comprising a calcined hydrotalcite catalyst. Said proposed system, as well as the additional subject matter of the present invention comprising an integrated process for producing ethyl acetate, acetaldehyde, hydrogen and ethylene, also include steps of dehydrogenation and dehydration, separation and obtaining the desired products, allowing the solvents to be reused in subsequent steps. The multi-product production system has two preferential configurations, which allow lower consumption of solvents, and at the same time reduce energy consumption. Consequently, the final products produced are highly pure, and produced by means of a highly efficient process and with efficient use of energy. The present invention is therefore an alternative for the alcohol-based chemical industry, especially industries that produce highly pure solvents.

Description

"INTEGRATED SYSTEM FOR THE PRODUCTION OF ETHYL ACETATE, ACETALDEHYDE, HYDROGEN AND ETHYLENE, INTEGRATED PROCESS FOR ETHYL ACETATE, ACETALDEHYDE, HYDROGEN AND ETHYLENE, AND PRODUCTS SO OBTAINED"

FIELD OF INVENTION

The present invention describes an integrated system for producing ethyl acetate, acetaldehyde, hydrogen, ethylene and water from ethanol. The proposed system, as well as the only integrated process for obtaining multi-products of interest and high commercial value, ensure greater efficiency of solvent use and energy use. Preferred embodiments of the present invention allow for lower solvent consumption as they advantageously have a single azeotropic mixture and produce a large number of products from ethanol at atmospheric pressure, thereby reducing energy consumption. environment in relation to existing technologies. Accordingly, the present invention is an alternative to the alcoholic productive sector, especially those producing high purity solvents, in addition to generating hydrogen, a clean energy source.

BACKGROUND OF THE INVENTION

The Brazilian industrial sector produces ethylene, ethylene oxide, butanol, octanol, acetaldehyde, acetic acid, ethyl acetate, butyl acetate, butadiene and other smaller scale products from ethanol. Part of the applied technology is not recent, but local, since the sugarcane industry has always reasonably supplied the market with ethanol and thus its use as a raw material in the chemical industry dates back to 1920 (JEWUR, SS, A. Química Nova, p.67, 1984) and (MENEZES, TJB, Ethanol the fuel of Brazil, Agronomical Publisher Ceres, 1980). According to the state of the art, the production of a particular product from ethanol is observed, unlike that proposed in the present invention, which generates multiproducts. Ethylene is the precursor of a wide range of products depending on the process in which it is employed. Some ethylene or ethylene derivatives are described by (SOUZA, AM, SOUSA-AGUIAR, EF Chemistry and Derivatives, p.64, 1983).

Patent application PI8205956-0 of 10/13/1982 deals with the production of ethylene from ethanol employing a vapor phase phosphoric acid based catalyst. Only the catalyst is described and not the subsequent separation steps or the conversion obtained by it.

Two documents describe the conversion of ethanol to ethylene, PI8504106-8 of 08/27/1985 and PI8700422-4 of 01/30/1987. The first document employs a zeolite-type catalyst containing a metal-substituted silicate and to maintain full conversion of ethanol it is necessary to regulate the catalyst temperature and the starting material flow rate. The second one specifically employs a crystalline aluminosilicate zeolite type catalyst. In these cases, just as the previous one describes only the catalyst and not the subsequent separation steps nor the conversion obtained by it. In contrast, the present invention is an integrated system describing two complete configurations for the production of hydrogen, ethyl acetate and acetaldehyde. In addition, the catalyst employed has acidic and basic characteristics which also generates in the process ethylene, water and hydrogen.

WO2007063279 of 06/07/07 describes the integrated production of ethylene and propylene from propanol in the vapor phase. Disadvantageously, the process is carried out in 7 columns and in two reactors, but in the present invention the process involves 4 or 5 columns for producing not only ethylene from ethanol but also hydrogen, ethyl acetate and acetaldehyde, and advantageously rectify the solvent.

Another process for producing ethylene from ethanol is described in patent application EP1792885 of 11/29/2005. The reaction involved is dehydration of ethanol generating ethyl ether and ethylene, employing 4 columns with great energy expenditure. Dehydration processes generate water and consequently azeotropy between water and ethanol, in addition to ether azeotropy. ethylene with water, consuming large amounts of energy in the separations to produce only two products. The new process proposed here also generates some water as it is an acid-base catalyst, however ethanol is totally consumed without having problems with azeotropy with water, and separating part of acetaldehyde that also has azeotropy with ethyl ether in a 99.9% pure columns.

Acetaldehyde is also raw material for a large amount of derivatives such as acetic acid, butanol, acetic anhydride MVA, PVA and polyvinyl alcohol (SOUZA, A.M., SOUSA-AGUIAR, E.F. Chemistry and Derivatives, p.64, 1983).

Patent Application CN1706550 of April 14, 2005 relates to a type of catalyst employed in one step of the ethyl acetate-ethanol synthesis process and its preparation and application process. The ammoniotiomolibidate catalyst is prepared by sulfurizing the catalyst with a specific sulfur and aluminum ratio. ^~ Besides ethyl acetate, also generates acetaldehyde this process, however the catalyst preparation is complex, which may cause problems in conversions of ethyl acetate. Unlike described herein, in the present invention the reaction is dehydrogenation and occurs in a gas phase, producing, in addition to ethyl acetate and acetaldehyde, hydrogen, a clean energy source.

US6399812 of April 27, 2000 describes the conversion of ethanol to ethyl acetate employing palladium impregnated zeolite catalysts. The reactor reaction mixture is separated by three column azeotropic distillation to recover the ethyl acetate product and the acetaldehyde and acetic acid byproducts. Disadvantageously, the described process uses solvents for the separation of compounds, generates residues that must be treated, in addition to carbon dioxide. Already in the present invention the catalyst employed is cheaper than the zeolitic one and if we take into account the palladium employed then it becomes even more expensive. In addition, the reactions of the present invention generate hydrogen and water without adding any reagent other than ethanol at atmospheric pressure. Ethyl acetate is a commercially important chemical. It is especially suitable as a solvent for extraction processes in the food industry and is used in the preparation of cosmetics, glues and paints. High purity ethyl acetate is also used as an intermediate in chemical syntheses.

One of the most commonly used processes for the production of ethyl acetate is the esterification reaction between acetic acid and ethanol. In US6693213 of 11/10/2000 ethyl acetate is produced from ethanol and acetic acid and / or acetic anhydride in the presence of an acid catalyst. Unlike the proposed invention, a single column catalytic distillation is performed and the maximum achieved purity of ethyl acetate was 96.1%. Already in the present invention it is a multi-process system which, besides producing ethyl acetate, generates acetaldehyde, hydrogen and ethylene with high purity.

The process of US2003013908 of December 22, 1999 also produces ethyl acetate from the reaction of acetic acid with ethanol in the presence of an acid catalyst. Further, a distillation step of the formed vapors, followed by condensation to form an organic phase rich in ethyl acetate and an aqueous phase rich in water, is described. At least a portion of the organic phase of the first distillation is directed to a separation membrane, which removes water, alcohol, or the combination of water and alcohol, from the ethyl acetate-rich organic phase. In addition to being an acidic process as described in the aforementioned patent, i.e. dehydrating, impairing yield, water separation employing membranes is an expensive and difficult to maintain process.

Patent Application CN 16 6398 of 09/14/2004 relates to a process of producing ethyl acetate by a tower of rectification tower with rectifying effect. After the reaction of acetic acid and ethanol, catalyzed by sulfuric acid, the solution is gasified forming an azeotrope system of ester, alcohol, water and acid, which is rectified and the products separated in an esterification tower. Ethyl acetate is provided with 95% purity.

Another reaction described for obtaining ethyl acetate is in patent application PI0511050-5 of 05/06/2005, which reacts ethylene and acid disadvantageously also employing an acid catalyst as described above. The process of said invention involves specific ratios of reactant concentrations in the reactor inlet streams and, if these values are changed, undesired products may be formed. The proposed invention differs from PI0511050-5 in that it is a vapor phase process at atmospheric pressure in a fixed bed reactor, being fed only with ethanol. The generated products are separated in conventional columns, only the last one is fed solvent to separate the ethyl acetate from the water, because the mixture has azeotropy.

WO2010014145-A2 of 07/20/2009 describes one of the methods employed for the production of ethyl acetate involving an acetic acid hydrogenation reaction. The reaction cited in this patent application occurs at high temperatures (225 to 275 ° C), with pressure between 10 and 20 atm and utilizes a bimetallic catalyst. The conversion of acetic acid using the catalysts of the invention is at least 20% and can be up to 70%, with ethyl acetate selectivity of at least 60%, preferably 80% and more preferably 95%. The proposed invention differs from that disclosed in WO2010014145-A2 in that it comprises an integrated system and process for obtaining ethyl acetate and other derivatives such as acetaldehyde, ethylene and hydrogen, and utilizing as a single reaction solvent. The present invention makes use of solvent which advantageously promotes the separation of ethyl acetate from water, which exhibit azeotropy when in binary mixing. The proposed system ensures the use of thermal energy promoting energy savings, as well as milder operating conditions compared to the technology deposited in 2009.

Another patent application which also describes an acetic acid hydrogenation reaction is EP0192587-A1 of 01/30/1986. The reaction in this case is catalyzed by ruthenium deposited on a silica support at high temperatures (250 to 350 ° C) and pressures (30 to 100 atm). The present invention differs from the European patent application in that it does not use the same catalyst, ruthenium being a high cost catalyst. Our catalyst operates at slightly above atmospheric pressure, as well as being a dehydrogenation reaction of ethanol generating ethyl acetate, acetaldehyde and ethylene, in addition to hydrogen, which can be used to generate energy.

Another method employed for the production of ethyl acetate is described in patent application PI0300729-4 of 12/03/2003 and involves a zirconium supported copper catalyst reaction. The proposed invention differs from that presented in PI0300729-4 in that it comprises a system and an integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene. The proposed system ensures the utilization of thermal energy promoting energy saving, besides milder operating conditions. compared to the technology deposited in 2003, it also advantageously uses solvent only to separate ethyl acetate from water, and the hydrogen produced that can be used to generate clean energy without carbon dioxide.

Another patent application which also describes the production of ethyl acetate is EP990638-A1 of 10/01/1998. Disadvantageously, the reaction in this case occurs at high pressures (6 to 30 bar), in addition to hydrogen recirculation. The present invention differs from this patent application in that it generates multiproducts and hydrogen does not need to be recirculated to promote optimal catalyst conditions, so it can be used in power generation and thus provide the process with part of the energy required for its catalyst. operation.

Three documents deal with the separation of ethyl acetate from ethanol and water. Patent Application CN1526692 of 09/22/2003 describes the separation with the use of recycles in the extractive column, obtaining a 97% purity content for ethyl acetate.

Already patent application CN1706799 of 11/05/2005 deals with separation employing salts and an extraction agent in a column with rectifying sections of the compounds. The ethyl acetate produced is 99.5% pure and about 95% ethanol.

And in WO200044696 of 01/28/1999 the separation process occurs by extractive distillation in the presence of a distillation solvent extractive material selected from a dimethyl sulfoxide, an amine, an alkylated thiophene or a paraffin.

In contrast to the three processes described above, in the present invention ethanol is fully consumed and the amount of water formed is relatively small which makes it possible to separate ethyl acetate with also a smaller amount of solvent, and some water remains in the ether. ethyl acetate and acetaldehyde that form azeotropy.

In view of the described technologies, the present invention has advantages in various aspects. Firstly, by using two possible new system configurations that encompass all stages of the process of producing ethyl acetate, acetaldehyde, hydrogen, ethylene and water from ethanol, employing gaseous fixed bed reaction means and secondly, by obtaining products such as pure hydrogen, ethylene and ethyl acetate. In addition, acetaldehyde can also be mostly purified in one of the proposed models.

Another advantage is that ethyl acetate is obtained from the dehydrogenation reaction of anhydrous ethanol without the use of high pressures. Additionally, a single solvent is employed to separate ethyl acetate from water at the end of the process. Two configurations are also proposed to produce 99.1 to 99.9 purity acetaldehyde, having a higher energy expenditure according to the required purity. The present invention addresses the need to preserve the environment with zero emission of pollutants.

The present invention comprises reaction media selected from fixed bed reactors. The fixed bed reactor has advantages over other types of configurations. Simplicity of operation due to bedding of particles, low construction and maintenance costs, little need for ancillary equipment as it does not require costly downstream catalyst separation units, and wide operating flexibility are among these advantages.

The difficulties usually related to the use of fixed bed reactors mainly refer to heat transfer. This is because the rate of energy release over the length of the reactor It is not uniform and most of the reaction usually occurs near the reactor inlet. Some devices to overcome these difficulties are known. One is the use of multitubular reactors, as used by McGreavy and Maciel Filho (McGreavy, C; Maciel Filho, R. 3rd Latin American Conf. Heat and Mass, Mexico, 1988), being just one way to properly modify the physical condition of the bed. Some devices are used to reduce the thermal effects of the reaction, such as the use of inert diluents in the feed, as well as the catalyst dilution with inert solid material. The control of the external refrigerant temperature and the division of the bed into independent sections also allows to adequately control the internal reactor temperature (Domingues, A. Ethanol Oxidation Process Modeling and Simulation Acetaldehyde, Campinas, SP. Faculty of Chemical Engineering, Campinas State University, 1992; Maciel Filho, R.; Domingues, A. ISCRE 12 - Twelfth International Symposium on Chemical Reaction Engineering, Turin, Italy, 1992).

Regarding the catalyst, mixed cobalt and aluminum oxide catalysts derived from the calcination of hydrotalcite materials were used. Hydrotalcite-type materials calcined at 500 and 650 ° C form mixed mesoporous oxides. (ARAÚJO M.C., Use of Hydrotalcites Mg / Co / Al in Ethanol Conversion, Master's Dissertation, Faculty of Chemical Engineering, State University of Campinas, 112p, 2003).

Nitrogen adsorption studies to observe pore distribution have found two pore-forming regions for 100% cobalt materials which, as they are calcined at higher temperatures, have only a pore diameter distribution, ie at 650 ° C, and this calcination no longer showed the formation of butanol and butyraldehyde and only traces of ethyl ether with higher amounts of acetaldehyde> ethyl acetate> ethylene. Probably, the larger cylindrical or spherical pores tend to generate dehydrogenation and closer proximity of cobalt and aluminum to the acid characteristic for ethylene formation in these materials (ARAÚJO MC, Utilization of Hydrotalcitas Mg / Co / Al in Conversion). Ethanol, Master's Dissertation, Faculty of Chemical Engineering, State University of Campinas, 112p, 2003).

The present invention advantageously employed this type of material derived from calcined hydrotalcites at 650 ° C because they are relatively easy to prepare and characterize to obtain mesoporous or commonly called nanometric materials. This mixed oxide catalyst obtained with calcination at 650 ° C had the advantage of preferentially promoting the dehydrogenation of acetaldehyde and ethyl acetate by generating a greater amount of hydrogen and reducing the amounts of ethyl ether to a trace, showing that the process Dehydration occurs only for small molecules, such as ethylene, and also generates smaller amounts of water. In the case of cobalt mixed oxides, a larger quantity of reactor tubes is necessary to ensure the conversion of all the ethanol fed, besides being disadvantageously classified as toxic, class II materials, and also, cobalt is a mineral little found. in Brazil, should always be imported ..

One of the most energy-consuming processes in a chemical industry is separation processes involving formed mixtures that have minimum or maximum azeotropes, as in these cases the use of solvents, pressure, new columns and refluxes should be added. In addition, the choice of solvent should be such as to ensure non-toxicity of the plant. In this regard, the present invention provides an alternative system and integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen, ethylene and water, with an emphasis on minimizing energy expenditure and reusing the solvents used therein.

BRIEF DESCRIPTION OF THE INVENTION

The present invention contemplates an integrated process for producing ethyl acetate, acetaldehyde, hydrogen, ethylene and water. A multiproduct procurement system in two preferred configurations. A further object of the present invention are the high purity products obtained by the processes described herein. The invention describes an integrated process comprising dehydrogenation and ethanol dehydration reaction steps, separating and obtaining the desired products by conferring solvent reuse in subsequent steps.

The configuration of said integrated system comprising this process is called a. The reaction step of said process occurs with a catalyst and ethanol feed into the reactor (PFRHIDRO) called step (a). The steps of separating said process comprise: a step of separating acetaldehyde and ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN); after reaction step (a) named (b1); a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained at (b1) in the column top stream (COLUMNI) called (b2); a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMA3), obtained at (b1) in the column bottom stream (COLUNAI) called (b3); a separation between water (column top) and ethylene glycol (column bottom) (COLUM4) obtained at (b3) in the column bottom stream (COLUM4) called step (b4). The step of obtaining pure ethylene comprises the step of separating the ethylene (column top) from acetaldehyde (column bottom) (COLUMA2), obtained from (b1) in the column top stream (COLUMAI), according to step ( b2), called step (d). To obtain acetaldehyde (bottom of the column) it was separated from the ethylene (top of the column) (COLUMA2), obtained from (b1) in the column top stream (COLUNAI), according to step (b2), called step ( d1). The step of obtaining pure ethyl acetate, called step (e1), comprises the removal of water (bottom of the column) from the ethyl acetate (top of the column) (COLUMA3) obtained at (b1) in the bottom of the column ( COLUMN) with ethylene glycol addition according to step (b3). And obtaining hydrogen, called step (f1) comprises flash separation of the other products after reaction step (a).

A second integrated process configuration for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene is described. The configuration of said integrated system comprising this process is called β. THE The reaction step of said process occurs with a catalyst and with the feed of ethanol into the reactor (PFRHIDRO) called step (a). The mixture separation step comprises a sequence of steps as described below: a separation step between a fraction of acetaldehyde and ethylene (top of the column) and ethyl acetate with water and another fraction of acetaldehyde (bottom of the column) (COLUMN ); after reaction step (a) called step (fc>1); a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained at (b1) in the column top stream (COLUMNI) called step (b2); a separation between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMA3), obtained at (b1) in the column bottom stream (COLUNAI) called step (b3); a separation between ethyl acetate (column top) and water with ethylene glycol (column bottom) (COLUMA4), obtained at (b3) in the column bottom stream (COLUMA3) called step (b4); a separation of water (top of the column) and ethylene glycol (bottom of the column) (COLUMN5), obtained at (b4) in the column bottom stream (COLUMN4) called step (b5). The pure ethylene step comprises the step of separating the ethylene (column top) from acetaldehyde (column bottom) (COLUMA2), obtained from (b1) in the column top stream (COLUMAI), according to step ( b2), called step (d). The step for obtaining ethyl acetate takes place in two columns, one of them from the separation of acetaldehyde (bottom of the column) from ethylene (top of the column) (COLUNA2), obtained from (b1) in the top of the column (COLUNAI) stream. ), according to step (b2), called step (d1); a second column in which acetaldehyde (top of the column) separation of ethyl acetate with water (column bottom) (COLUMA3) obtained from (b1) in the column bottom stream (COLUNAI) according to step (b3) occurs ), called step (d2). The step of obtaining pure ethyl acetate, called step (e1), comprises the removal of water (bottom of the column) from the ethyl acetate (top of the column) (COLUMA4) obtained from (b3) in the bottom stream of the column ( COLUMN3) with ethylene glycol addition according to step (b4). And obtaining hydrogen, called step (f1) comprises the flash separation of the other products after reaction step (a).

The integrated ethyl acetate, acetaldehyde, hydrogen, ethylene production system, by configuration a, comprises at least one fixed bed reaction medium with calcined hydrotalcite type catalyst; at least four mixture separation means; separating means comprising at least one additional solvent stream preferably ethylene glycol; heat exchange means selected from parallel and countercurrent exchange between currents resulting from the process itself; means for mixing solvents and reagents; catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment and monitoring of catalytic bed pressure drop; and, available hydrogen separation means.

The integrated ethyl acetate, acetaldehyde, hydrogen and ethylene production system by the β configuration comprises at least one fixed bed reaction medium with calcined hydrotalcite catalyst; at least five mixture separation means; separating means comprising at least one additional solvent stream preferably ethylene glycol; means for exchanging heat selected from parallel and countercurrent exchange between currents resulting from the process itself; means for mixing solvents and reagents; catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment and monitoring of catalytic bed pressure drop; and available hydrogen separation means. BRIEF DESCRIPTION OF THE FIGURES

Figure 1: System with configuration a.

Figure 2: System with β configuration.

Figure 3: Molar composition of the multitubular reactor for dehydrogenation and dehydration of ethanol 10,000 tubes configuration a.

DETAILED DESCRIPTION OF THE INVENTION

The present invention describes an integrated system for producing ethyl acetate, acetaldehyde, hydrogen and ethylene. The ethyl acetate production process by fixed bed reaction with mixed cobalt and aluminum oxide catalysts derived from calcination of hydrotalcite and separation means in arrangements configured for maximum efficiency, solvent recovery and energy, according to said proposed system, result in products with good specification levels.

Said integrated system comprises two configurations selected from system operating with five distillation columns and system operating with only four. In both configurations ethyl acetate, acetaldehyde, hydrogen and ethylene are obtained.

Said embodiments operate with a solvent to separate ethyl acetate from water, said solvent may preferably be ethylene glycol.

In the present invention, we call said four-column operating system α and said five-column operating system we call β. The catalyst selected was calcined hydrotalcite at 650 ° C composed of cobalt and aluminum, as it was more selective in relation to the products obtained (ethylene, acetaldehyde, ethyl acetate, hydrogen and traces of ethyl ether). For the purposes of the names in this report, an azeotropic mixture occurs when the composition of the liquid phase is equal to the composition of the vapor phase for a given point on the equilibrium curve. When the bubble point temperature is equal to the dew point temperature and corresponds to the lowest temperature value in the diagram, the azeotrope is called the minimum boiling azeotrope. Otherwise, that is, the highest value for the temperature in the diagram, the azeotrope, is called the maximum boiling point azeotrope.

Additionally the present invention comprises an integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene whose preferred operating conditions are described below.

It is a further object of the present invention the high purity products, preferably between 95.5% and 99.9%, obtained by said integrated process according to each of the proposed system configurations. Said products are ethyl acetate, acetaldehyde, hydrogen and ethylene.

The so-called α system separates acetaldehyde into just one solvent-free column as the catalyst has a residual ether production which will remain in acetaldehyde due to the azeotropy between them.

The system called β separates acetaldehyde into two columns without the use of solvents.

The integrated ethyl acetate, acetaldehyde, hydrogen and ethylene production system, in both α and β configurations, can alternatively comprise catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment assisting in heat removal chemical reaction by convection and monitoring of pressure drop in the catalytic bed.

Said catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment and monitoring of the catalytic bed pressure drop may preferably be by feeding a nitrogen stream with a certain flow rate to remove impurities from the catalytic bed. catalytic bed as well as maintaining the temperature at 350 ° C. And only after this nitrogen feed should the ethanol feed be started.

Said separation means are preferably distillation columns.

Said fixed bed reaction means is preferably of the multitubular type and the available hydrogen separation means, preferably flash or membrane reactor.

The operating temperature of multitubular reactors is dependent on the type of catalyst and the type of reaction involved in the process.

In the exemplary embodiments of the present invention, multitubular fixed bed reactors of 2 meters in length and 5.08 centimeters in diameter (termed PFRHIDRO reactor) were selected without, however, restricting the present invention.

The plant has many products, but these are easily separable. The separation of ethyl acetate from ethanol presents the greatest difficulty, since they form an azeotropic mixture with minimum boiling point, which is located close to half the molar concentration of both. Ethylene does not present any difficulty of separation, whatever your concentration. And with respect to the acetaldehyde ethanol blend, the higher the acetaldehyde concentrations in ethanol, the more easily they will be separated.

To avoid the azeotropic ternaries: ethanol / ethyl acetate / water, the number of reactor tubes in the proposed plants was increased for the catalysts derived from these calcined hydrotalcite-type materials at 650 ° C, thus virtually all of the ethanol reacted.

Another problem would be the separation of hydrogen from other products, which would normally occur at very low temperatures (from -187 ° C to -192 ° C). But to avoid this fact a flash (called FLASH1), a simple liquid vapor separation system was used to remove hydrogen from the system. A hydrogen permeable membrane reactor could also be employed in the proposed flash replacement system.

As the formation of minimal boiling azeotropy between acetaldehyde and ethyl ether will occur, the best separation should occur using molecular sieves, given the large difference in molecule size rather than the use of solvents. This implies a great operational complexity and as the amounts of ethyl ether are minimal this separation is not proposed in this present invention.

The boiling points of the compounds found in the literature

(Prausnitz et al., 2001 The Properties of Gases and Liquids; Bruce E. Poling.,

John M. Prausnitz., John P. O'Connell 15th Edition) are in Table 1.

Table 1: Boiling points (Prausnitz et al., 2001) (1,01325 bar).

The concern in obtaining the pure product is a demand of the new plant projects and the adequacy of the existing plants. And, using the catalyst versatility and, on the other hand, knowing the importance of obtaining water within environmental specifications, the present invention describes an integrated ethyl acetate, acetaldehyde, hydrogen and ethylene production system comprising two configurations for dehydrogenation and dehydration of the vapor-phase ethanol that differ only in the separation process employed to obtain acetaldehyde.

Configuration (a)

The following description comprises a preferred embodiment of the present invention without limitation. Said integrated process for producing ethyl acetate, acetaldehyde, hydrogen and ethylene comprises the following steps:

(a) ethanol dehydrogenation and dehydration reaction with a catalyst and reactor ethanol feed (PFRHIDRO);

(b) separating mixtures comprising:

(b1) a separation between ethylene acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN) after reaction step (a);

(b2) a separation between ethylene (column top) and acetaldehyde (column bottom) (COLUMN2), obtained from (b1) in the column top stream (COLUMNI);

(b3) a separation between ethyl acetate (top of the column) and water with ethylene glycol (column bottom) (COLUMA3) obtained from (b1) in the column bottom stream (COLUNAI);

(b4) a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMA4) obtained from (b3) in the column bottom stream (COLUMA3).

(c) obtaining ethylene comprising:

(d) separation of ethylene (column top) from acetaldehyde (column bottom) (COLUMA2) obtained from (b1) in the column top stream (COLUMAI) and consequently obtaining pure ethylene according to step (b2) .

(d) obtaining acetaldehyde comprising: (d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMN2) obtained from (b1) in the column top stream (COLUMNI) and consequently obtaining pure acetaldehyde according to step (b2) .

(e) obtaining ethyl acetate comprising:

(e1) removal of water (bottom of the column) from ethyl acetate (top of the column) (COLUMA3) obtained from (b1) in the column bottom stream (COLUNAI) with the addition of ethylene glycol and thereby obtaining pure ethyl acetate according to step (b3);

(f) obtaining hydrogen comprising:

(f1) separating, by means of separation, the other products after reaction step (a).

Said exemplary embodiment of the present invention is intended to further clarify the process without, however, restricting it. Process (a) according to the foregoing description comprises an ethanol feed stream in reaction step (a) having a preferred inlet pressure of 1.355 bar and a preferred temperature of 350 ° C with 32 kmol / h of ethanol. In this example the configuration is proposed with a mixer for possible bed maintenance steps, since nitrogen feed is not used in the reaction step, but this can be used in case of operating star-up for a temperature stabilization of fixed reactor bed.

Separation step (b) comprised a separation step (b1) between ethylene acetaldehyde (top of the column) and ethyl acetate with water

(column bottom) (COLUMN) in a preferred temperature range between 13 and 70 ° C, a preferential atmospheric pressure and preferably in 24 stages, the feed plate being 14 °, with a reflux ratio 0.8 and background rate of 10.69 kmol / h.

In the exemplary embodiments, the separation step (b2) between ethylene

(top of the column) and acetaldehyde (bottom of the column) (COLUMN2) considered a preferred temperature range between -105 to 20 ° C, an atmospheric pressure, and preferably in 16 stages, with the feed plate 8 ^o of reflux 1 and distilled rate 4.09 kmol / h. The present process in the α configuration comprises a solvent feed preferably ethylene glycol during separation (b3) between ethyl acetate (top of the column) and water (bottom of the column) (COLUMA3) obtained at (b1) in the bottom of the column (COLUNAI) stream. ) and, consequently obtaining pure ethylene to a preferred range of temperature of 75 at 120 ° C, atmospheric pressure and preferably at 52 stages, and the feed plate the 43 ° and the solvent feed plate 11 ^a, with reflux ratio 0.52 and distilled rate of 6.49 kmol / h with liquid / liquid / vapor convergence.

With respect to the separation step (b4) between water (top of the column) and ethylene glycol (bottom of the column) (COLUMA4) obtained at (b3) in the column bottom current (COLUMA3), the preferred temperature is selected from 98 to 195 5 ° C and atmospheric pressure, and preferably at 22 stages, being the feed plate 7, with a reflux ratio 0.54 and background rate 4.4 kmol / h.

Advantageously the solvent (ethylene glycol) resulting from step (b4) is recovered and recirculated and can again feed the separation step of COLUMN 3. The water in the proposed system is considered a noble product of the process because if it comes out pure when In the end the process is totally efficient and the energy costs are calculated on water.

A further object of the present invention is an integrated ethyl acetate acetaldehyde, hydrogen and ethylene production system in an a configuration comprising:

(a) at least one fixed bed reaction medium with calcined hydrotalcite catalyst;

(b) at least four mixture separation means;

(b1) separating means comprising at least one additional solvent stream;

(c) heat exchange means;

(d) means for mixing solvents and reagents;

(e) catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment and monitoring of catalytic bed pressure drop; (f) available hydrogen separation means.

A preferred system configuration comprises:

(a) at least one reaction medium preferably multitubular fixed bed reactor with calcined hydrotalcite catalyst;

(b) at least four mixture separation means preferably distillation columns;

(b1) separating means comprising at least one distiller fed with an additional stream of solvent preferably ethylene glycol;

(c) means of exchanging heat selected from parallel and countercurrent exchange preferably indirect countercurrent heat exchangers between currents resulting from the process itself;

(d) means for mixing solvents and reagents;

(e) catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment, and monitoring of the catalytic bed pressure drop preferably be by supply with a nitrogen stream in element (a), as the pressure it is related to the conversion of ethanol;

(f) available hydrogen separation means, preferably flash or membrane reactor.

For a better understanding of this system, the configuration named a is available in Figure 1.

Configuration (β)

The present invention comprises an integrated process for producing ethyl acetate, acetaldehyde, hydrogen and ethylene, the configuration of which (β) comprises the following steps:

(b) separating mixtures comprising:

(b1) a separation between a fraction of preferably 15% ethylene acetaldehyde (top of the column) and ethyl acetate with water and another fraction with preferably 85% of acetaldehyde (column bottom) (COLUMN) after reaction step (a);

(b3) a separation between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMA3) obtained from (b1) in the bottom of the column (COLUNAI) stream;

(b4) a separation between ethyl acetate (top of the column) and water with ethylene glycol (column bottom) (COLUMA4) obtained from (b3) in the column bottom stream (COLUMA3);

(b5) a separation between water (column top) and ethylene glycol (column bottom) (COLUMA5) obtained from (b4) in the column bottom stream (COLUMA4).

(c) obtaining ethylene comprising:

(Cl) separation of ethylene (column top) from acetaldehyde (column bottom) (COLUMA2), obtained from (b1) in the column top stream (COLUMAI) and consequently obtaining pure ethylene according to step (b2) .

(d) obtaining acetaldehyde comprising:

(d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMA2) obtained from (b1) in the column top stream (COLUMAI) and consequently obtaining pure acetaldehyde according to step (b2) ;

(d2) separation of acetaldehyde (top of the column) from ethyl acetate with water (column bottom) (COLUMA3) obtained from (b1) in the column bottom stream (COLUNAI) and consequently obtaining pure acetaldehyde according to step (b3).

(e) obtaining ethyl acetate comprising:

(e1) removal of water (bottom of column) from ethyl acetate (top of column) (COLUMA4) obtained from (b3) in the column bottom stream (COLUMA3) with the addition of ethylene glycol and thereby obtaining pure ethyl acetate according to step (b4);

(f) obtaining hydrogen comprising: (f1) separating, by means of separation, the other products after reaction step (a).

In the exemplary embodiments of the present invention, without restricting the scope thereof, contemplates an ethanol feed stream in reaction step (a) with a preferred pressure of 1.255 bar, a preferred temperature of 350 ° C and preferably with 50 kmol / h ethanol, with a catalytic bed pressure drop of 0.3 bar.

In this example the configuration is proposed with a mixer for possible bed maintenance steps, since nitrogen feed is not used in the reaction step, but this can be used in case of operating star-up for a temperature stabilization of fixed reactor bed.

The separation step (b) comprised a separation step (b1) between a preferably 15% fraction of acetaldehyde with ethylene (top of the column) and ethyl acetate with water and the largest preferably 85% fraction of acetaldehyde (bottom). (COLUMN) in a preferred temperature range of -5 to 33 ° C, a preferred pressure of 0.955 bar and preferably in 32 stages, the feed plate being 1 1 ^o , reflux ratio 3, 01 and distillate rate of 10.24 kmol / h.

In the separation step (b2) between ethylene (top of the column) and acetaldehyde

(bottom of column) (Column2) at a preferred temperature range of - 105 to 20 ° C, atmospheric preferred pressure, preferably at 16 stages, and the feed plate the 8th with reflux ratio 1 and ratio of 6.56 kmol / h distillate.

The separation step (b3) between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMA3) obtained at (b1) in the column bottom current (COLUNAI) occurs within a preferred temperature range between 20 and 70 ° C, a preferential atmospheric pressure and preferably in 50 stages, the feed plate being 39 °, with reflux ratio 1 and distillate rate of 20.0 Kmol / h, with liquid / liquid / vapor convergence. .

The step of obtaining pure ethyl acetate (e1) comprises feeding a solvent preferably ethylene glycol during separation. (b4) between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUNA4) obtained from (b3) in the column top stream (COLUNA3) and thereby obtaining pure ethyl acetate in a temperature range from 75 to 118 ° C, a preferred pressure of 0.955 bar and preferably in 52 stages, with the feed plate 44 ° and the solvent feed plate 11 °, with reflux ratio 0.54 and distillate rate 9.74 kmol / h, with liquid / liquid / vapor convergence.

The separation (b5) between water (column top) and ethylene glycol (column bottom) (COLUMA5) obtained at (b4) in the column bottom stream (COLUMA4) occurs in a preferred temperature range between 98 and 195.5 °. C is a preferential pressure of 0.955 bar and preferably in 22 stages, the feed plate being 7 °, with reflux ratio of 0.54 and bottom rate of 6.79 kmol / h.

Advantageously the solvent (ethylene glycol) resulting from step (b5) is recovered and recirculated, and can again feed the separation step of COLUMN 4. The water in the proposed system is considered a noble product of the process, because if it comes out pure when In the end the process is totally efficient and the energy costs are computed to water.

A further object of the present invention is an integrated ethyl acetate, acetaldehyde, hydrogen and ethylene production system characterized by a β configuration as can be seen in Figure 2, comprising:

(a) at least one fixed bed reaction medium with calcined hydrotalcite catalyst;

(b) at least five mixture separation means;

(b1) separating means comprising at least one additional solvent stream;

(c) heat exchange means;

(d) means for mixing solvents and reagents;

It is a preferred embodiment of the present invention a system comprising:

(b) at least five mixture separation means preferably distillation columns;

(c) means of exchanging heat selected from parallel and countercurrent exchange, preferably indirect countercurrent heat exchangers between currents resulting from the process itself;

(d) means for mixing solvents and reagents;

(f) available hydrogen separation means, preferably flash or membrane reactor.

For a better understanding of this system, the configuration called β is available in Figure 2.

99.99% high purity ethyl acetate obtained according to any of the processes for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene described above.

High purity 95.5 to 99.9% acetaldehyde obtained according to any of the processes for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene described above.

99.9% high purity ethylene obtained according to any of the processes for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene described above. 100% pure hydrogen obtained according to any of the systems for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene described above.

Example 1 - Integrated system for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene in a configuration named a.

The so-called α system comprises reaction media with calcined hydrotalcite type catalyst at 650 ° C in a fixed-phase vapor bed reactor where anhydrous ethanol is fed without nitrogen. Said reactor is called PFRHIDRO reactor. In a preferred configuration, without, however, restricting the PFRHIDRO reactor, to meet a production of approximately 5,000 tons / year of ethyl acetate may comprise 10,000 tubes, with dimensions of (2m x 2 ").

In the present example, without, however, restricting the reactor inlet molar flows are at a temperature of 350 ° C and a pressure of 1, 355 bar and consist of ethanol equal to 32 kmol / h. The pressure drop across the reactor is 0.4 bar.

Figure 3 shows the molar compositions along the cobalt hydrotalcite reactor, PFRHIDRO, as a function of reactor length for plant a. It can be seen that practically, after 60 cm of reactor, all the ethanol was consumed. However, according to industry practice, the reactor should be designed to be 10 to 30 percent longer than the minimum length to ensure longer run time.

Example 2 - Integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen, ethylene and water employing the system a.

The exemplary embodiment described below shows a reaction step wherein said step comprises a catalyst preferably of calcined hydrotalcite type and ethanol feed. The temperature of the reactor in said non-restricting embodiment, however, was 350 ° C.

Table 2 shows an example embodiment of the present invention showing the inlet and outlet streams of the cobalt hydrotalcite reactor for plant a. It is also possible to check the operating temperature and pressure drop in the reactor. Table 2: Input and output currents in the cobalt hydrotalcite reactor, where EREATOR is reactor input current, SREATOR is reactor output current.

In the present embodiment example, the separation step is intended to purify the obtained product which is in mixtures formed in earlier stages of the multiproduct production process. Column 1 is a typical azeotropic distillation column, acetaldehyde and ethylene having minimal boiling azeotropy come out at the top of the column and at the bottom of the column in stream FUND01 there is ethyl acetate and water. An interesting factor is the amount of water that can be removed at the bottom of the column along with acetic acid. This column has a 24 stage configuration, with the feed plate 14 ° and reflux ratio 0.8, with 99.99% acetaldehyde along with 100% ethylene leaving the top of the column.

Column 2 in the present example is a conventional distillation column, this column is intended to separate acetaldide from ethylene. Ethylene is separated at the top of the distillation column with a molar composition purity of 99.9%. Acetaldehyde remains at the bottom of the distillation column with a molar composition of 99.1%. Column 2 is a conventional convergence column cryogenic (low temperature), preferably composed of 16 stages and the feed plate 8 is ⁰ to 1. The reflux ratio has minimal ethyl ether azeotroping point boiling with acetaldehyde and cannot be separated remaining as a residue in acetaldehyde.

Column 3 in this example is a special, differentiated extractive column. It can be said to be an extractive column because the solvent in this case disrupts the ethyl acetate / water azeotropy due to the formation of the two distinct liquid phases in the mixture capturing the water remaining at the bottom of the column along with the solvent. in stream FUND03 and thus proceeding to a rectifying column for recovery of the pure solvent. Ethyl acetate is separated at the top of the distillation column with a molar composition purity of 99.9%. Water and solvent remain at the bottom of the distillation column. Column 3 has 52 stages, the FUND01 current feed plate is 43 ° and the SOLVENT current feed plate is 11 °, with a reflow ratio of 0.52.

Column 4 is a conventional distillation column for solvent rectification having 22 stages; the preferred feeding plate being 12 ° and operating at a reflux ratio of 0.54. The AGUAP top stream has 100% pure water, the solvent remains at the bottom of the column in the SOLVENTP stream, also 100% pure.

The pure solvent obtained at the bottom of column 4 is passed through the SOLVENTETP stream to the TROCA3 exchanger to take advantage of the thermal energy released by reducing the temperature that will facilitate separation in the next column, hence it is driven by the SOLVENT stream to column 3.

Example 3 - Integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen, ethylene and water according to the β system.

In the β plant configuration there is a higher energy expenditure, as it has five columns. This system separates acetaldehyde into two columns allowing, without the use of solvents, to obtain it with a purity of 99.87% for the column that separates most of the acetaldehyde and 95.5% for the column where it was sent the largest. part of the ethyl ether residue produced.

The first column is a conventional distillation column with 32 stages, the feed plate 11 is, the reflux ratio is 3.01. It is a column that It takes more energy to make a small amount of acetaldehyde carry most ethyl ether with it.

In column 2 of the present example, ethylene remains at the top of the distillation column with a purity of 99.9% molar composition and at the bottom of the column has most ethyl ether remaining together with acetaldehyde with a 95.5% molar composition due to minimum boiling azeotropy as seen above between acetaldehyde and ethyl ether. It is a conventional column with cryogenic convergence and has 16 stages, the feed plate is 8 ^o and the reflux ratio 1.

Column 3 is an azeotropic distillation column. The column will have three phases: two liquid and one vapor phase, having 50 stages, the feed plate is 39 ° and the reflux ratio 1. Acetaldehyde remains at the top of the distillation column with a purity of molar composition. 99.87%, with the ethyl ether residue being impurity, and at the bottom of the column is ethyl acetate and water.

The steam molar composition of column 4 in the present example is similar to that of column 3 of configuration a, a special extractive column.

At the top of the distillation column comes ethyl acetate of 99.9% molar composition purity. The column 52 has four stages, the feed plate of o11 is ^the solvent stream and the feed plate FUND03 the current is 44 ° and the reflux ratio 0.54.

The fifth column is a conventional distillation column for the rectification of the solvent, with 22 stages and the feed plate is 7, with a reflux ratio of 0.54. The AGUA top stream features 100% water; the solvent remains at the bottom of the column in the SOLVENT stream of 100% purity.

This column 5 is exactly the same as column 4 of plant a, so the water comes out pure at the end, the process is totally efficient and the energy costs are computed to water, and the solvent is recovered and re-circulated to the process at this stage.

Claims

1 / 8O 2013/029129 PCT / BR2011 / 000458 CLAIMS

1. Integrated process for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water, comprising the following steps:

(b) separating mixtures comprising:

(c) obtaining ethylene comprising:

(d) obtaining acetaldehyde comprising:

(d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMN2) obtained from (b1) in the column top stream (COLUMNI) and consequently obtaining pure acetaldehyde according to step (b2) .

(e) obtaining ethyl acetate comprising:

(f) obtaining hydrogen comprising: 2/8

The 2013/029129 PCT / BR2011 / 000458

Process according to Claim 1, characterized in that the feed stream in reaction step (a) comprises a preferential pressure of 1, 355 bar and a preferential temperature of 350 ° C.

Process according to Claim 2, characterized in that the reaction step comprises a feed stream preferably with 32 kmol / h of ethanol.

Process according to Claim 1, characterized in that the separation step (b) comprises a separation step (b1) between ethylene acetaldehyde (top of the column) and water-ethyl acetate (bottom of the column) (COLUMN). in a preferred temperature range between 13 and 70 ° C, a preferred atmospheric pressure and preferably in 24 stages.

Process according to any one of Claims 1 to 4, characterized in that it comprises a step of separating (b2) between ethylene.

(column top) and acetaldehyde (column bottom) (COLUMN2) in a preferred temperature range between -105 to 20 ° C, an atmospheric pressure, and preferably in 16 stages.

Process according to Claim 1, characterized in that it comprises feeding a preferably ethylene glycol solvent during separation (b3) between ethyl acetate (top of the column) and water (bottom of the column) (COLUMA3) obtained in (b1). in the column bottom stream (COLUMN) and consequently obtaining pure ethylene glycol.

Process according to Claim 6, characterized in that it comprises a preferred temperature range of 75 to 120 ° C, an atmospheric pressure and preferably in 52 stages.

Process according to Claim 1, characterized in that it comprises a separation (b4) between water (top of the column) and ethylene glycol (bottom of the column) (COLUMA4) obtained from (b3) in the bottom of the column (COLUMA3) stream. at a temperature between 98 and 95.5 ° C, an atmospheric pressure and preferably in 22 stages. 3/8

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Process according to Claim 8, characterized in that the ethylene glycol is recovered and recirculated and can again feed the separation step of COLUMN 3.

10. An integrated ethyl acetate, acetaldehyde, hydrogen, ethylene and water production system characterized by an α configuration comprising:

(a) at least one fixed bed reaction medium with calcined hydrotalcite catalyst;

(b) at least four mixture separation means;

(b1) separating means comprising at least one additional solvent stream;

(c) heat exchange means;

(d) means for mixing solvents and reagents;

(e) catalytic bed cleaning or activation means, line cleaning, reaction temperature adjustment and monitoring of catalytic bed pressure drop;

(f) available hydrogen separation means.

System according to Claim 10, characterized in that it comprises at least one reaction medium, preferably a fixed bed multitubular reactor with calcined hydrotalcite-type catalyst.

System according to Claim 10, characterized in that it comprises at least four mixture separation means, preferably distillation columns.

System according to Claim 10, characterized in that it comprises separation means comprising at least one distiller supplied with an additional solvent stream preferably ethylene glycol.

System according to claim 10, characterized in that it comprises heat exchange means selected from parallel and countercurrent exchange, preferably indirect countercurrent heat exchangers between currents resulting from the process itself. 4/8

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System according to Claim 10, characterized in that it comprises means for cleaning or activating catalytic bed, line cleaning, reaction temperature adjustment and monitoring of pressure drop in the catalytic bed, preferably by feeding with a current. nitrogen in element (a);

System according to Claim 10, characterized in that it comprises available hydrogen separation means, preferably flash or membrane reactor.

System according to claim 10, characterized in that said configuration α comprises a process according to the claims of

1 to 9.

18. An integrated process for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water comprising the following steps:

(b) separating mixtures comprising:

(b1) a separation between a fraction with preferably 15% ethylene acetaldehyde (top of the column) and another fraction with preferably 85% ethyl acetate with water (column bottom) (COLUMN) after reaction step (a );

(b5) a separation between water (column top) and ethylene glycol (column bottom) (COLUMA5) obtained from (b4) in the column bottom stream (COLUMA4). 5/8

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(c) obtaining ethylene comprising:

(d) obtaining acetaldehyde comprising:

(e) obtaining ethyl acetate comprising:

(f) obtaining hydrogen comprising:

Process according to claim 13, characterized in that the feed stream in reaction step (a) comprises a preferential pressure of 1.255 bar and a preferred temperature of 350 ° C.

Process according to Claim 14, characterized in that the reaction step comprises a feed stream preferably containing 50 kmol / h of ethanol.

Process according to Claim 13, characterized in that the separation step (b) comprises a separation step between a fraction with preferably 15% acetaldehyde and ethylene (top of the column) and ethyl acetate with water and another fraction with preferably 85% acetaldehyde (column bottom) (b1) (COLUMN) in a preferred range of 6/8

The temperature is between -5 and 33 ° C, a preferential pressure of 0.955 bar and preferably in 32 stages.

Process according to Claim 13, characterized in that it comprises a step of separating (b2) between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2) in a preferred temperature range between -105 to 20 °. C is a preferential atmospheric pressure and preferably in 16 stages.

Process according to Claim 13, characterized in that it comprises a step of separating (b3) between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN3) obtained from (b1) in the flow stream. column bottom (COLUMN) in a preferred temperature range between 20 and 70 ° C, a preferred atmospheric pressure and preferably in 50 stages.

Process according to claim 13, characterized in that obtaining pure ethyl acetate (e1) comprises feeding a solvent preferably ethylene glycol during separation (b3) between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMA4) obtained from (b3) in the column top stream (COLUMA3) and, consequently obtaining pure ethyl acetate, in a preferred temperature range of 75 to 118 ° C, a preferred pressure of 0.955 bar and, preferably in 52 stages.

Process according to Claim 13, characterized in that it comprises a separation (b5) between water (column top) and ethylene glycol (column bottom) (COLUMA5) obtained from (b4) in the column bottom stream (COLUMA4). in a preferred temperature range between 98 and 195.5 ° C, a preferred pressure of 0.955 bar and preferably in 22 stages.

Process according to Claim 20, characterized in that the ethylene glycol is recovered and recirculated and can again feed the separation step of COLUMN 4.

27. An integrated ethyl acetate, acetaldehyde, hydrogen, ethylene and water production system characterized by a β configuration comprising: 7/8

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(a) at least one fixed bed reaction medium with calcined hydrotalcite catalyst;

(b) at least five mixture separation means;

(b1) separating means comprising at least one additional solvent stream;

(c) means of exchange;

(d) means for mixing solvents and reagents;

(f) available hydrogen separation means.

System according to claim 27, characterized in that it comprises at least one reaction medium, preferably a fixed bed multitubular reactor with calcined hydrotalcite-type catalyst;

System according to claim 27, characterized in that it comprises at least five mixture separation means, preferably distillation columns.

A system according to claim 27, characterized in that it comprises separation means comprising at least one distiller supplied with an additional solvent stream preferably ethylene glycol.

System according to Claim 27, characterized in that it comprises heat exchange means selected from parallel and countercurrent exchange, preferably indirect countercurrent heat exchangers between currents resulting from the process itself.

System according to claim 27, characterized in that it comprises means for cleaning or activating catalytic bed, line cleaning, reaction temperature adjustment and monitoring of pressure drop in the catalytic bed, preferably by feeding with a current. nitrogen in element (a). 8/8

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System according to claim 27, characterized in that it comprises available hydrogen separation means, preferably flash or membrane reactor.

System according to claim 27, characterized in that said configuration β comprises a process according to the claims of

18 to 26.

Ethyl acetate which is obtained with a preferential purity of between 99.9% and 100% according to any of the processes described in claims 1 and 18.

Acetaldehyde characterized in that it is obtained with a purity of from 95.5 to 99.9% according to any of the processes described in claims 1 and 18.

Ethylene characterized in that it is obtained with preferential purity between 99.9% and 100% according to any of the processes described in claims 1 and 18.

Pure hydrogen characterized in that it is obtained according to any of the processes described in claims 1 and 18.