BRPI1104013B1 - INTEGRATED SYSTEM FOR THE PRODUCTION OF ETHYL ACETATE, ACETALDEHYDE, HYDROGEN AND ETHYLENE, INTEGRATED PROCESS FOR OBTAINING ETHYL ACETATE, ACETALDEHYDE, HYDROGEN AND ETHYLENE - Google Patents

Abstract

integrated system for the production of ethyl acetate, acetaldehyde, hydrogen and ethylene, integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene and products thus obtained. The present invention describes an integrated system for obtaining high added value ethyl acetate, acetaldehyde, hydrogen and ethylene from a process involving reaction step comprising a calcined hydrotalcite type catalyst. said proposed system as well as the additional object of the present invention comprising an integrated process for the production of ethyl acetate, acetaldehyde, hydrogen and ethylene, additionally contains dehydrogenation and dehydration steps, separation and obtaining the desired products, conferring solvent reuse in stages. subsequent The multi-product procurement system features two preferred configurations that allow lower solvent consumption while reducing energy consumption. Thus, the final products obtained are of high purity, in a process of high efficiency and energy efficiency. therefore, the present invention is an alternative to the alcoholic productive sector especially those producing high purity solvents.

Description

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

FIELD OF THE INVENTION

The present invention describes an integrated system for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water from ethanol. The proposed system, as well as the only integrated process for obtaining multiproducts of interest and of high commercial value, guarantee greater efficiency in the use of solvents and energy use. The preferred configurations of the present invention allow a lower consumption of solvents, since, advantageously, they present a single azeotropic mixture and produce a large number of products from ethanol, at atmospheric pressure, reducing energy consumption, consequently, this invention contributes to the environment in relation to existing technologies. Therefore, the present invention is an alternative for the alcohol-chemical production sector, especially those that produce 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 products on a smaller scale 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, therefore, 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, Editora Agronômica Ceres, 1980). According to the state of the art, the production of a certain product from ethanol is observed, differently from what is proposed in the present invention, which generates multi-products.

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Ileno ethylene is a precursor to a wide range of products depending on the process in which it is used. Some derivatives of ethylene or ethylene are described by (SOUZA, A.M., SOUSA-AGUIAR, E.F. Química e Derivados, p, 64, 1983).

Patent application PI8205956-0 of 10/13/1982 deals with the production of ethylene from ethanol using a catalyst based on phosphoric acid in the vapor phase. 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 uses a zeolite-type catalyst containing a metal-substituted silicate and to maintain the total conversion of ethanol, it is necessary to regulate the temperature of the catalyst and the flow rate of the starting material. The second one specifically employs a crystalline aluminosilicate zeolite type catalyst. In these cases, just like the previous one, only the catalyst is described and not the subsequent separation steps or the conversion obtained by it. In contrast, the present invention deals with an integrated system, describing two complete configurations, for the production of hydrogen, ethyl acetate and acetaldehyde. In addition, the catalyst used has acidic and basic characteristics that also generates ethylene, water and hydrogen in the process.

Document W02007063279 of 07/06/07 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, in the present invention the process involves 4 or 5 columns for the production not only of ethylene from ethanol, but also of hydrogen, ethyl acetate and acetaldehyde, besides being 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, using 4 columns with great energy expenditure. Dehydration processes generate water and, as a result, azeotropy between water and ethanol, in addition to ether azeotropy

3/27 ethyl with water, consuming large amounts of energy in the separations to produce only two products. The new process proposed here also generates some water for being an acid-base catalyst, however ethanol is totally consumed without presenting problems of azeotropy with water, in addition to separating part of the acetaldehyde which also presents azeotropy with ethyl ether in a columns with 99.9% purity.

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

Patent application CN1706550 of 4/14/2005 refers to a type of catalyst used in a stage of the ethyl acetate synthesis process with ethanol and its preparation and application process. The ammoniotiomolybidate catalyst is prepared based on sulfurization of the catalyst with a specific sulfur and aluminum ratio. In addition to ethyl acetate, this process also generates acetaldehyde, but the preparation of the catalyst is complex, which can lead to problems in ethyl acetate conversions. Unlike what is described in this document, in the present invention the reaction is dehydrogenation and occurs in the gas phase, producing, in addition to ethyl acetate and acetaldehyde, hydrogen, a source of clean energy.

The US6399812 patent of 4/27/2000 describes the conversion of ethanol into ethyl acetate, using palladium-impregnated zeolite catalysts. The reaction mixture of the reactor is separated by azeotropic distillation in three columns to recover the ethyl acetate product and the by-products acetaldehyde and acetic acid. Disadvantageously, the described process uses solvents to separate the compounds, generates residues that must be treated, in addition to carbon dioxide. In the present invention, however, the catalyst used is cheaper than the zeolite and if we take into account the palladium used then it becomes even more expensive. In addition, the reactions of the present invention generate hydrogen and water without adding any reagents other than ethanol, at atmospheric pressure.

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Ethyl acetate is a commercially important chemical. It is especially indicated as a solvent for extraction processes in the food industry, in addition to being 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 used processes for the production of ethyl acetate is the esterification reaction between acetic acid and ethanol. In the 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, catalytic distillation is performed on a single column and the maximum purity achieved for ethyl acetate was 96.1%. In the present invention, however, it is a multi-process system, which in addition to producing ethyl acetate, generates acetaldehyde, hydrogen and ethylene with high purities.

The patent application process US2003013908 of 12/22/1999 also produces ethyl acetate from the reaction of acetic acid with ethanol, in the presence of an acid catalyst. In addition, a step of distillation of the formed vapors is described, followed by condensation to form an organic phase rich in ethyl acetate and an aqueous phase rich in water. At least part 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 organic phase rich in ethyl acetate. In addition to being an acidic process, as described in the patent cited above, that is, dehydrating, impairing performance, water separation using membranes is an expensive and difficult to maintain process.

Patent application CN1616398 of 14/09/2004 relates to a process for the production of ethyl acetate by means of a tower esterification tower with rectification effect. After the reaction of acetic acid and ethanol, catalyzed by sulfuric acid, the solution is gasified forming an ester, alcohol, water and acid azeotrope system, which is rectified and the products separated in an esterification tower. Ethyl acetate is supplied with 95% purity.

Another reaction described for obtaining ethyl acetate is found in patent application PI0511050-5 dated 06/05/2005, which reacts ethylene and acid

5/27 acetic, also disadvantageously employing an acid catalyst, as described above. The process of said invention involves specific relationships of the concentrations of the reactants in the inlet currents of the reactor and, if these values are changed, unwanted products can 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 in the last one solvent is fed to separate ethyl acetate from water, due to the mixture having azeotropy.

WO2010014145-A2 of 20/07/2009 describes one of the methods used for the production of ethyl acetate, involving a hydrogenation reaction of acetic acid. The reaction mentioned in this patent application occurs at high temperatures (225 to 275 ° C), with pressure between 10 and 20 atm and uses a bimetallic catalyst. The conversion of acetic acid using the catalysts of the invention is at least 20% and can reach 70%, with selectivity for ethyl acetate of at least 60%, preferably 80% and more preferably 95%. The proposed invention differs from that presented in W02010014145-A2, as it comprises an integrated system and process for obtaining ethyl acetate and other derivatives such as acetaldehyde, ethylene and hydrogen, in addition to using a single solvent as the reaction solvent. The present invention makes use of a solvent that advantageously promotes the separation of ethyl acetate from water, which has an azeotropic point when in binary mixture. The proposed system guarantees the use of thermal energy, promoting energy savings, in addition to smoother operating conditions when compared to the technology deposited in 2009.

Another patent application that also describes a hydrogenation reaction of acetic acid 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, with ruthenium being a high cost catalyst. Our catalyst operates

6/27 a pressure slightly above atmospheric pressure, in addition to 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 used for the production of ethyl acetate is described in patent application PI0300729-4 of 12/03/2003 and involves a reaction based on copper catalysts, supported on zirconium. The proposed invention differs from that presented in PI0300729-4, as it comprises a system and an integrated process for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene. The proposed system guarantees the use of thermal energy promoting energy savings, in addition to milder operational conditions when compared to the technology deposited in 2003, in addition to advantageously using solvent only to separate ethyl acetate from water, and the hydrogen produced that can be used to generate clean energy without the presence of carbon dioxide.

Another patent application that also describes the production of ethyl acetate is EP990638-A1 of 10/1/1998. 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 multi-products and the hydrogen does not need to be recirculated to promote the optimum conditions of the catalyst, so it can be used in the generation of energy and thus provide the process with part of the energy necessary for its operation.

Three documents deal with the separation of ethyl acetate from ethanol and water. Patent application CN 1526692 of 22/09/2003 describes the separation using recycles in the extractive column, obtaining a 97% purity content for ethyl acetate.

The patent application CN1706799 of 11/05/2005 deals with the separation using salts and an extraction agent in a column with compound rectification sections. The ethyl acetate produced is 99.5% pure and ethanol around 95%.

And in document W0200044696 of 01/28/1999 the separation process occurs by extractive distillation in the presence of a distillation solvent

7/27 extractive 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 completely consumed and the amount of water formed is relatively small, which makes it possible to separate ethyl acetate with an even smaller amount of solvent, and a little water remains in the ether ethyl and acetaldehyde that form azeotropy.

In view of the technologies described, the present invention has advantages in several aspects. First, by using two possible configurations of an unprecedented system that encompass all the stages of the production process of ethyl acetate, acetaldehyde, hydrogen, ethylene and water from ethanol, using means of reaction via fixed bed in gaseous state and second, 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. In addition, a single solvent is used to separate ethyl acetate from water at the end of the process. Two configurations are also proposed to produce acetaldehyde with 99.1 to 99.9 purity, presenting a higher energy expenditure according to the required purity. The present invention meets 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 the fixation of particles in the bed, with low construction and maintenance cost, little need for auxiliary equipment, as it does not require costly units for separating the downstream catalyst, and wide operating flexibility are among these advantages.

The difficulties usually related to the use of fixed bed reactors refer mainly to heat transfer. This is due to the fact that the rate of energy release along the length of the reactor

8/27 is not uniform and most of the reaction normally occurs in the vicinity of the reactor inlet. Some devices for overcoming these difficulties are known. One of them 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 of the ways to modify appropriately. 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, and also the dilution of the catalyst with inert solid material. The temperature control of the external refrigerant and the division of the bed in independent sections also allow to adequately control the internal temperature of the reactor (Domingues, A. Modeling and Simulation of Ethanol Oxidation Process to Acetaldehyde, Campinas, SP. Faculdade de Engenharia Química, State University of Campinas, 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-type materials were used. Hydrotalcite-type materials calcined at 500 and 650 ° C form mixed mesoporous oxides. (ARAÚJO M.C., Use of Hydrotalcites Mg / Co / AI in Ethanol Conversion, Master's Dissertation, Faculty of Chemical Engineering, State University of Campinas, 112p, 2003).

In the nitrogen adsorption studies to observe the pore distribution, two pore formation regions were found for materials with 100% cobalt which, as they are calcined at higher temperatures, present only a pore diameter distribution, ie at 650 ° C, and in this calcination, the formation of butanol and butyraldehyde was no longer present and only traces of ethyl ether with greater amounts of acetaldehyde> ethyl acetate> ethylene. Probably, the larger cylindrical or spherical pores tend to generate dehydrogenation and the greater proximity of cobalt and aluminum to the acid characteristic for the formation of ethylene in these materials (ARAÚJO M.C., Use of Hydrotalcites Mg / Co / AI in Conversion

9/27 Ethanol, Master's Dissertation, Faculty of Chemical Engineering, State University of Campinas, 112p, 2003).

The present invention advantageously employed this type of material from hydrotalcites calcined at 650 ° C because they are relatively easy to prepare and characterize, obtaining 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, generating a greater amount of hydrogen and reducing, in traces, the amounts of ethyl ether, showing that the process dehydration occurs only for small molecules, such as ethylene, and also generating less water. In the case of mixed cobalt oxides, a greater number of reactor tubes is needed to guarantee the conversion of all ethanol fed, in addition to being disadvantageously classified as toxic, class II materials, and yet, cobalt is a little-found mineral. in Brazil, and should always be imported ..

One of the most energy-consuming processes in a chemical industry is the separation processes involving formed mixtures that present minimum or maximum azeotropes, since in these cases the use of solvents, pressure, new columns and refluxes must be added. In addition, the choice of the solvent must be such that it guarantees the non-toxicity of the plant. In this sense, the present invention presents 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 during it.

BRIEF DESCRIPTION OF THE INVENTION

The present invention contemplates an integrated process for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water. A system for obtaining multi-products in two preferred configurations. High purity products obtained by the processes described herein are an additional object of the present invention.

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The invention describes an integrated process comprising reaction steps of dehydrogenation and dehydration of ethanol, separation and obtaining the desired products, conferring solvent reuse in subsequent steps.

The configuration of said integrated system comprising this process is called α. The reaction step of said process occurs with a catalyst and ethanol supply in the reactor (PFRHIDRO) called step (a). The separation steps of said process comprise: a separation step between acetaldehyde and ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN1); after reaction step (a) called (b1); a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) called (b2); a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN3), obtained in (b1) in the bottom column current (COLUMN1) called (b3); a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN 4) obtained in (b3) in the chain at the bottom of the column (COLUMN 3) called step (b4). The step of obtaining pure ethylene comprises the step of separating ethylene (top of the column) from acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1), according to step ( b2), called step (c1). To obtain acetaldehyde (bottom of the column) it was separated from ethylene (top of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1), according to step (b2), called step ( d1). The step of obtaining pure ethyl acetate, called step (e1), involves the removal of water (bottom of the column) from ethyl acetate (top of the column) (COLUMN3) obtained in (b1) in the bottom of the column ( COLUMN1) with the addition of ethylene glycol, according to step (b3). And obtaining hydrogen, called step (f 1) comprises the separation, through the flash, of the other products after the 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

11/27 the reaction step of said process takes place with a catalyst and with the ethanol supply in the reactor (PFRHIDRO) called step (a). The step of separating the mixtures comprises a sequence of steps as described below: a step of separating a fraction of acetaldehyde and ethylene (top of the column) and ethyl acetate with water and another fraction of the acetaldehyde (bottom of the column) (COLUMN1 ); after reaction step (a) called step (b1); a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) called step (b2); a separation between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN3), obtained in (b1) in the current at the bottom of the column (COLUMN1) called step (b3); a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN4), obtained in (b3) in the current at the bottom of the column (COLUMN3) called step (b4); a separation of water (top of the column) and ethylene glycol (bottom of the column) (COLUMNS), obtained in (b4) in the chain at the bottom of the column (COLUMN4) called step (b5). The step of obtaining pure ethylene comprises the step of separating ethylene (top of the column) from acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the top column current (COLUMN1), according to step ( b2), called step (c1). The step of obtaining ethyl acetate occurs in two columns, one from the separation of acetaldehyde (bottom of the column) from ethylene (top of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1 ), according to step (b2), called step (d1); a second column in which the separation of acetaldehyde (top of the column) from ethyl acetate with water (bottom of the column) (COLUMN 3) obtained in (b1) in the bottom column current (COLUMN 1), according to step (b3) ), 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) (COLUMN 4) obtained in (b3) in the stream of the bottom of the column ( COLUMN3) with the addition of ethylene glycol, according to step (b4). And obtaining hydrogen, called step (f1)

12/27 comprises the separation, via flash, of the other products after the reaction step (a).

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

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

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 10000 tubes configuration a.

DETAILED DESCRIPTION OF THE INVENTION

The present invention describes an integrated system for the production of ethyl acetate, acetaldehyde, hydrogen and ethylene. The ethyl acetate production process by means of a fixed bed reaction with mixed cobalt and aluminum oxide catalysts derived from the calcination of materials of the type

13/27 hydrotalcite and separation means in arrangements configured for maximum efficiency, recovery of solvents and energy, according to a proposed system, result in products with good levels of specification.

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

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

In the present invention, we call said system that operates with four columns as α and said system that operates with five we call β. The selected catalyst was hydrotalcite calcined at 650 ° C composed of cobalt and aluminum, since 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 of this specification, 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 point azeotrope. Otherwise, that is, the higher temperature value in the diagram, the azeotrope, is called the maximum boiling point azeotrope.

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

It is an additional object of the present invention to products with high purity, 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 system called α separates acetaldehyde in only one column without using solvents, since the catalyst has a residual ether production

14/27 ethyl that will remain in acetaldehyde due to the azeotropy between them.

The system called β separates acetaldehyde into two columns without using solvents.

The integrated production system for ethyl acetate, acetaldehyde, hydrogen and ethylene, in both α and β configurations, can alternatively comprise means of cleaning or activating catalytic bed, cleaning the line, adjusting the reaction temperature helping to remove heat chemical reaction by convection and monitoring the pressure drop in the catalytic bed.

Said means of cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed can be preferentially by feeding a nitrogen stream, with a certain flow to remove impurities. of the catalytic bed as well as maintaining the temperature at 350 ° C. It is only after this nitrogen supply that ethanol should be started.

Said separation means are preferably distillation columns.

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

The operating temperature of multitubular reactors depends 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 with a length of 2 meters and 5.08 cm in diameter (called a 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, as they form an azeotropic mixture with a minimum boiling point, which is located close to half the molar concentration of both. Ethylene, on the other hand, does not present any separation difficulties,

15/27 whatever your concentration. And with respect to the acetaldehyde ethanol mixture, the higher the concentrations of acetaldehyde in ethanol, the more easily they will be separated.

To avoid azeotropic ternaries: ethanol / ethyl acetate / water, the number of reactor tubes in the proposed plants was increased for catalysts from these hydrotalcite-type materials calcined at 650 ° C, thus practically 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, a flash (called FLASH1) was used, a simple liquid vapor separation system to remove hydrogen from the system. A membrane reactor permeable to hydrogen could also be used in the proposed system to replace the flash.

As the formation of azeotropy with a minimum boiling point between acetaldehyde and ethyl ether will occur, the best separation should occur using molecular sieves, given the large difference in the size of the molecules, and not through the use of solvents. This implies 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).

Compound TebuliçãoLIT [° C] Hydrogen 252.88 Ethanol 78.65 Acetaldehyde 21.06 Ethyl Acetate 77.06 Ethylene -103.73 Ethyl ether 34.44 Water 100.00

The concern with obtaining the pure product is a demand for new plant projects and the adequacy of existing plants. And, using the

16/27 catalyst versatility and, on the other hand, knowing the importance of obtaining water within environmental specifications, the present invention describes an integrated production system for ethyl acetate, acetaldehyde, hydrogen and ethylene comprising two configurations for dehydrogenation and dehydration of ethanol in the vapor phase, which differ only in the separation process used to obtain acetaldehyde.

Configuration (a)

The description that follows comprises a preferred embodiment of the present invention, without, however, restricting it. The said integrated production process for ethyl acetate, acetaldehyde, hydrogen and ethylene comprises the following steps:

(a) ethanol dehydrogenation and dehydration reaction with a catalyst and ethanol supply in the reactor (PFRHIDRO);

(b) separation of mixtures comprising:

(b1) a separation between acetaldehyde with ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN1) after reaction step (a);

(b2) a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1);

(b3) a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN3) obtained in (b1) in the chain at the bottom of the column (COLUMN1);

(b4) a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN 4) obtained in (b3) in the chain at the bottom of the column (COLUMN 3).

(c) obtaining ethylene comprising:

(c1) separation of ethylene (top of column) from acetaldehyde (bottom of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequent obtaining of pure ethylene, according to step (b2) .

(d) obtaining acetaldehyde comprising:

17/27 (d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequently obtaining pure acetaldehyde, according to step (b2).

(e) obtaining ethyl acetate comprising:

(e1) removal of water (bottom of column) from ethyl acetate (top of column) (COLUMN3) obtained in (b1) in the bottom column (COLUMN1) with the addition of ethylene glycol and, consequently, obtaining pure ethyl acetate , according to step (b3);

(f) obtaining hydrogen comprising:

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

Said embodiment example of the present invention is intended to better clarify the process, without, however, restricting. The process (a) according to the previous description comprises a feed stream with ethanol in the reaction step (a) with a preferred inlet pressure of 1.355 bar and a preferred temperature of 350 ° C with 32 kmol / h of ethanol. In the above example, the configuration is proposed with a mixer for eventual bed maintenance steps, since no nitrogen supply is used in the reaction step, but this can be used in cases of operation star-up to stabilize the bed temperature. fixed reactor bed.

The separation step (b) comprised a separation step (b1) between acetaldehyde with ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN1) in a preferred temperature range between 13 and 70 ° C , a preferential atmospheric pressure and, preferably, in 24 stages, with the feed plate being 14 °, with a reflux ratio of 0.8 and a bottom rate of 10.69 kmol / h.

In the embodiment examples, the separation step (b2) between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2) considered a preferred temperature range between -105 and 20 ° C, an atmospheric pressure and, preferably at 16 stages, being the feed plate 8 with 1 reflux ratio , and distillate rate 4.09 kmol / h.

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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) (COLUMN3) obtained in (b1) in the bottom column current (COLUMN1 ) 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 of the feed plate 11 ^a, reflux ratio 0.52 and distillate rate 6.49 kmol / h with liquid / liquid / vapor convergence.

Regarding the separation step (b4) between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN4) obtained in (b3) in the bottom column current (COLUMN3), the preferred temperature is selected between 98 and 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, being able to feed again the separation phase 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 completely efficient and energy costs are computed using water.

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

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

(b) at least four means for separating mixtures;

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

(c) means of exchanging heat;

(d) means of mixing solvents and reagents;

(e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed;

19/27 (f) means of separating the available hydrogen.

A preferred system configuration comprises:

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

(b) at least four means for separating mixtures, preferably distillation columns;

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

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

(d) means of mixing solvents and reagents;

(e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and, monitoring the pressure drop in the catalytic bed, preferably through feeding with a nitrogen stream in element (a), because the pressure it is related to the conversion of ethanol;

(f) means of separating the available hydrogen, preferably flash or membrane reactor.

For a better understanding of said system, the configuration called a, is available in Figure 1.

Configuration (B)

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

(a) ethanol dehydrogenation and dehydration reaction with a catalyst and ethanol supply in the reactor (PFRHIDRO);

(b) separation of mixtures comprising:

(b1) a separation between a fraction with preferably 15% acetaldehyde with ethylene (top of the column) and ethyl acetate with water and another

20/27 fraction with preferably 85% acetaldehyde (bottom of column) (COLUMN1) after reaction step (a);

(b2) a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1);

(b3) a separation between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN3) obtained in (b1) in the current at the bottom of the column (COLUMN1);

(b4) a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN4) obtained in (b3) in the stream at the bottom of the column (COLUMN3);

(b5) a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMNS) obtained in (b4) in the chain at the bottom of the column (COLUMN4).

(c) obtaining ethylene comprising:

(c1) separation of ethylene (top of column) from acetaldehyde (bottom of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequent obtaining of pure ethylene, according to step (b2) .

(d) obtaining acetaldehyde comprising:

(d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequent obtaining of pure acetaldehyde, according to step (b2) ;

(d2) separation of acetaldehyde (top of column) from ethyl acetate with water (bottom of column) (COLUMN3) obtained in (b1) in the bottom column current (COLUMN1) 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) (COLUMN4) obtained in (b3) in the bottom of column column (COLUMN3) with the addition of ethylene glycol and, consequently, obtaining pure ethyl acetate , according to step (b4);

(f) obtaining hydrogen comprising:

21/27 (f1) separation, by means of separation, from the other products after the reaction step (a).

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

In the above example, the configuration is proposed with a mixer for eventual bed maintenance steps, since no nitrogen supply is used in the reaction step, but this can be used in cases of operation star-up to stabilize the bed temperature. fixed reactor bed.

The separation step (b) comprised a separation step (b1) between a fraction of preferably 15% of the acetaldehyde with ethylene (top of the column) and ethyl acetate with water and the largest fraction of preferably 85% of acetaldehyde (bottom) ) column (column1) at a preferred temperature range between - 5 was 33øC, a preferred pressure of 0.955 bar and preferably at 32 stages, being the feed plate 11, with a 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 the column) (COLUMN2) in a preferential temperature range between - 105 and 20 ° C, a preferential atmospheric pressure and, preferably in 16 stages, being the 8 ^o feed plate, with reflux ratio 1 and distillate rate of 6.56 kmol / h.

The separation step (b3) between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN3) obtained in (b1) in the current at the bottom of the column (COLUMN1) occurs in a preferential temperature range between 20 and 70 ° C, a preferred atmospheric pressure and, preferably in 50 stages, the feed plate being 39 °, with reflux ratio 1 and distillate rate of 20.10 Kmol / h, with liquid / liquid / vapor convergence .

The step of obtaining pure ethyl acetate (e1) comprises feeding a solvent preferably ethylene glycol during separation

22/27 (b4) between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN4) obtained in (b3) in the top column current (COLUMN3) and, consequently, obtaining pure ethyl acetate , in a preferential temperature range of 75 to 118 ° C, a preferential pressure of 0.955 bar and, preferably in 52 stages, the feed plate being 44 ° and the solvent feeding plate 11 °, with reflux ratio 0.54 and distillate rate 9.74 kmol / h, with liquid / liquid / steam convergence.

The separation (b5) between water (top of the column) and ethylene glycol (bottom of the column) (COLUMNS) obtained in (b4) in the current at the bottom of the column (COLUMN4) occurs in a preferred temperature range between 98 and 195.5 ° C, a preferential pressure of 0.955 bar and, preferably in 22 stages, the feed plate being the 7th, with a reflux ratio of 0.54 and a bottom rate of 6.79 kmol / h.

Advantageously the solvent (ethylene glycol) resulting from step (b5) is recovered and recirculated, being able to feed again the separation phase 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 completely efficient and energy costs are computed in water.

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

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

(b) at least five means for separating mixtures;

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

(c) means of exchanging heat;

(d) means of mixing solvents and reagents;

(e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed;

23/27 (f) means of separating the available hydrogen.

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

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

(b) at least five means for separating mixtures, preferably distillation columns;

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

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

(d) means of mixing solvents and reagents;

(e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and, monitoring the pressure drop in the catalytic bed, preferably through feeding with a nitrogen stream in element (a), because the pressure it is related to the conversion of ethanol;

(f) means of separating the available hydrogen, preferably flash or membrane reactor.

For a better understanding of said 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 acetaldehyde from 95.5 to 99.9% obtained according to any of the processes for obtaining ethyl acetate, acetaldehyde, hydrogen and ethylene described above.

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

24/27

100% pure hydrogen obtained according to any of the processes 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 called a.

The system called α comprises reaction means with a hydrotalcite catalyst calcined at 650 ° C in a fixed bed reactor in a vapor phase where anhydrous ethanol is fed without the presence of nitrogen. Said reactor is called a PFRHIDRO reactor. In a preferential configuration, without, however, restricting, the PFRHIDRO reactor, to serve a production of approximately 5,000 tons / year of ethyl acetate, may comprise 10,000 tubes, with dimensions of (2m x2 ”).

In the present example, without, however, restricting, the molar flow rates in the reactor are at a temperature of 350 ° C and 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 the reactor length for plant a. It can be seen that, practically, after 60 cm of reactor, all ethanol was consumed. However, according to industrial practice, the reactor must be designed between 10 to 30% more than the minimum length to guarantee a longer campaign time.

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

The embodiment example described below shows a reaction step, said step comprising a catalyst preferably of the calcined hydrotalcite type and ethanol feed. The temperature of the reactor, in said example of embodiment, without, however, restricting, was 350 ° C.

Table 2 shows an example of an embodiment of the present invention showing the inlet and outlet currents of the cobalt hydrotalcite reactor for plant a. It is also possible to check the operating temperature and pressure drop in the reactor.

25/27

Table 2: The input and output currents in the cobalt hydrotalcite reactor, where EREATOR is the reactor input current, SREATOR is the reactor output current.

EREATOR SREATOR ETHANOL 32 0.00221618 ACETALDEHYDE 0 14.6930743 ETHYLENE 0 4.0833932 ETHYL ACETATE 0 6.48229459 HYDROGEN 0 27.6576635 WATER 0 4.21175678 ETHYL ETHER 0 0.12836358 Total molar flow [kmol / h] 32 57.2587621 Total mass flow [kg / h] 1474.20928 1474.20928 Total volumetric flow rate [l / min] 22017,8472 51773,4587 Temperature [-C] 350 349.999992 Pressure [atm] 1.2385887 0.94251172

In the present example of embodiment, the separation step aims to purify the product obtained which is found in mixtures formed in previous stages of the process of obtaining the multi-products. Column 1 is a typical azeotropic distillation column, acetaldehyde and ethylene that have a minimum boiling point azeotropy come out at the top of the column and at the bottom of the column in the FUND1 stream there is ethyl acetate and water. An interesting factor is the amount of water that can be removed at the bottom of the column together with acetic acid. This column has a 24-stage configuration, the feed plate being 14 ° and the reflux ratio of 0.8, with 99.99% of acetaldehyde together with 100% of ethylene coming out at the top of the column.

Column 2, in the present example, is a conventional distillation column, this column aims to separate acetaldehyde from ethylene. Ethylene is separated at the top of the distillation column with 99.9% molar composition purity. The acetaldehyde remains at the bottom of the distillation column with a molar composition of 99.1%. Column 2 is a conventional column with cryogenic convergence (for low temperatures), preferably composed of 16 stages and the feed plate is the 8 ⁰ with reflux ratio 1. The ethyl ether has a minimum point of azeotropy

26/27 boiling with acetaldehyde and cannot be separated remaining as a residue in acetaldehyde.

Column 3, in said example, is a special, differentiated extraction column. It can be said that it is an extractive column, because the solvent, in this case, breaks the ethyl acetate / water azeotropy due to the formation of the two distinct liquid phases in the mixture capturing the water that remains at the bottom of the column together with the solvent in the FUNDO3 chain and, thus, proceeding to a rectification column to recover the pure solvent. The ethyl acetate is separated at the top of the distillation column with 99.9% molar composition purity. The water and solvent remain at the bottom of the distillation column. Lane 3 shows 52 stages of the feed plate FUNDO1 current is 43 ° and the solvent stream, the 11th, with reflux ratio of 0.52.

Column 4 is a conventional distillation column for the rectification of the solvent with 22 stages; the preferred feed plate is 12 ° and operates with a reflux ratio of 0.54. The AGUAP top stream contains 100% pure water, the solvent remains at the bottom of the column in the SOLVENTP stream, also with 100% purity.

The pure solvent obtained at the bottom of column 4 is conducted through the SOLVENTETP current to the EXCHANGER 3 exchanger to take advantage of the thermal energy released by reducing the temperature that will facilitate the separation in the next column, from there it is conducted by the SOLVENT current for 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 using solvents, obtaining it with a purity of 99.87% for the column that separates most of the acetaldehyde and 95.5% for the column where 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

27/27 consumes more energy to make a small amount of acetaldehyde carry most ethyl ether with it.

In column 2, of the present example, the ethylene remains at the top of the distillation column with a purity in terms of 99.9% molar composition and at the bottom of the column there is the majority of ethyl ether which remains together with the acetaldehyde with a 95.5% molar composition due to the minimum boiling point azeotropy as seen previously between acetaldehyde and ethyl ether. It is a conventional column with cryogenic convergence and has 16 stages, the feeding 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, with 50 stages, the feed plate is 39 ° and the reflux ratio 1. Acetaldehyde remains at the top of the distillation column with a purity in terms of molar composition 99.87%, the residue of ethyl ether being the impurity, and at the bottom of the column there is ethyl acetate and water.

The molar vapor 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, ethyl acetate comes out with 99.9% molar composition purity. Column 4 has 52 stages, the SOLVENT chain feed plate is 11 °, and the FUNDO3 chain feed plate is 44 ° and the reflux ratio is 0.54.

Column 5 is a conventional distillation column for the rectification of the solvent, with 22 stages and the feed plate is the 7th, with a reflux ratio of 0.54. The top stream AGUA has 100% water; the solvent remains at the bottom of the column in the SOLVENT stream with 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 on the water, and the solvent is recovered and re-circulated to the process at this stage.

Claims (34)

1. Integrated process for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water, characterized by comprising the following steps: (a) ethanol dehydrogenation and dehydration reaction with a catalyst and 5 ethanol feed in the reactor (PFRHIDRO); (b) separation of mixtures comprising: (b1) a separation between acetaldehyde with ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN1) after reaction step (a); 10 (b2) a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1); (b3) a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN3) obtained in (b1) in the stream at the bottom of the column (COLUMN1); (b4) a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN 4) obtained in (b3) in the chain at the bottom of the column (COLUMN 3). (c) obtaining ethylene comprising: 20 (c1) separation of ethylene (top of column) from acetaldehyde (bottom of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequent obtaining of pure ethylene, according to step (b2 ). (d) obtaining acetaldehyde comprising: (d1) separation of acetaldehyde (bottom of column) from ethylene (top of 25 column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequently obtaining pure acetaldehyde, according to step (b2). (e) obtaining ethyl acetate comprising: (e1) removal of water (bottom of column) from ethyl acetate (top of column) (COLUMN3) obtained in (b1) in the stream at the bottom of column 30 (COLUMN1) with the addition of ethylene glycol and, consequently, obtaining ethyl acetate pure, according to step (b3); (f) obtaining hydrogen comprising: Petition 870180140298, of 10/11/2018, p. 4/14 2/7 (f1) separation, by means of separation, from the other products after the reaction step (a). 2. Process according to claim 1, characterized by the supply current in the reaction step (a) comprising a pressure of 5 1,355 bar and a temperature of 350 ° C. Process according to claim 2, characterized by the reaction step comprising a feed stream with 32 kmol / h of ethanol. Process according to claim 1, characterized in that the separation step (b) comprises a separation step (b1) between acetaldehyde 10 with ethylene (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN 1) in a temperature range between 13 and 70 ° C, an atmospheric pressure and, in 24 stages. Process according to any one of claims 1 to 4, characterized in that it comprises a separation step (b2) between ethylene 15 (top of the column) and acetaldehyde (bottom of the column) (COLUMN2) in a temperature range between - 105 and 20 ° C, an atmospheric pressure and, in 16 stages. Process according to claim 1, characterized in that it comprises feeding an ethylene glycol solvent during separation (b3) between ethyl acetate (top of the column) and water (bottom of the column) 20 (COLUMN3) obtained in (b1) in the bottom column current (COLUMN1) and, consequently, obtaining pure ethylene glycol. Process according to claim 6, characterized in that it comprises a temperature range of 75 to 120 ° C, an atmospheric pressure and, in 52 stages. 25 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) (COLUMN 4) obtained in (b3) in the bottom of the column (COLUMN 3) at a temperature between 98 and 195.5 ° C, an atmospheric pressure and, in 22 stages. 30 9. Process according to claim 8, characterized by the ethylene glycol being recovered and recirculated, being able to feed again the separation phase of COLUMN 3. Petition 870180140298, of 10/11/2018, p. 5/14 3/7 10. Integrated production system for ethyl acetate, acetaldehyde, hydrogen, ethylene and water characterized by an α configuration comprising: (a) at least one fixed bed reaction medium with catalyst of the type 5 calcined hydrotalcite; (b) at least four means for separating mixtures; (b1) separation means comprising at least one additional solvent stream; (c) means of exchanging heat; (D) means of mixing solvents and reagents; (e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed; (f) means of separating the available hydrogen. 15 System according to claim 10, characterized in that it comprises at least one reaction medium, being this fixed bed multitubular reactor with calcined hydrotalcite catalyst. System according to claim 10, characterized in that it comprises at least four means for separating mixtures, these being, 20 distillation columns. System according to claim 10, characterized in that it comprises separation means comprising at least one distiller fed with an additional solvent stream, this being ethylene glycol. 14. The system according to claim 10, characterized in that it comprises means of exchanging heat selected from exchange in parallel and in countercurrent, these indirect heat exchangers being in countercurrent between currents resulting from the process itself. 15. System according to claim 10, characterized by means of cleaning or activating catalytic bed, line cleaning, 30 adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed by supplying a nitrogen stream in the element (a); Petition 870180140298, of 10/11/2018, p. 6/14 4/7 16. System according to claim 10, characterized by means of separating the available hydrogen, flash or membrane reactor. 17. System according to claim 10, characterized by said The α configuration comprises a process according to claims 1 to 9. 18. Integrated process for the production of ethyl acetate, acetaldehyde, hydrogen, ethylene and water, characterized by comprising the following steps: (a) ethanol dehydrogenation and dehydration reaction with a catalyst and 10 ethanol feed in the reactor (PFRHIDRO); (b) separation of mixtures comprising: (b1) a separation between a fraction with 15% acetaldehyde with ethylene (top of the column) and another fraction with 85% of the acetaldehyde with ethyl acetate and with water (bottom of the column) (COLUMN1) after reaction step (a) ; (B2) a separation between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1); (b3) a separation between acetaldehyde (top of the column) and ethyl acetate with water (bottom of the column) (COLUMN3) obtained in (b1) in the bottom 20 stream of the column (COLUMN1); (b4) a separation between ethyl acetate (top of the column) and water with ethylene glycol (bottom of the column) (COLUMN4) obtained in (b3) in the stream at the bottom of the column (COLUMN3); (b5) a separation between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN5) obtained in (b4) in the chain at the bottom of the column (COLUMN4). (c) obtaining ethylene comprising: (c1) separation of ethylene (top of column) from acetaldehyde (bottom of column) (COLUMN2), obtained in (b1) in the chain at the top of column (COLUMN1) 30 and consequent obtaining of pure ethylene, according to step (b2 ). (d) obtaining acetaldehyde comprising: Petition 870180140298, of 10/11/2018, p. 7/14 5/7 (d1) separation of acetaldehyde (bottom of column) from ethylene (top of column) (COLUMN2), obtained in (b1) in the chain at the top of the column (COLUMN1) and consequently obtaining pure acetaldehyde, according to step (b2); (d2) separation of acetaldehyde (top of column) from ethyl acetate with 5 water (bottom of the column) (COLUMN3) obtained in (b1) in the stream of the bottom of the column (COLUMN1) and consequently obtaining pure acetaldehyde, according to step (b3). (e) obtaining ethyl acetate comprising: (e1) removal of water (bottom of the column) from ethyl acetate (top of the 10 column) (COLUMN 4) obtained in (b3) in the stream at the bottom of the column (COLUMN 3) with the addition of ethylene glycol and, consequently, obtaining ethyl acetate pure, according to step (b4); (f) obtaining hydrogen comprising: (f1) separation, by means of separation, of the other products 15 after the reaction step (a). 19. System according to claim 13, characterized by the supply current in the reaction step (a) comprising a pressure of 1.255 bar and a temperature of 350 ° C. 20. The system according to claim 14, characterized by the reaction step comprising a feed stream with 50 kmol / h of ethanol. 21. System according to claim 13, characterized by the separation step (b) comprising a separation step between a fraction with 15% acetaldehyde and ethylene (top of the column) and ethyl acetate with water and another fraction with 85 % of acetaldehyde (bottom of column) (b1) (COLUMN1) in 25 a temperature range between - 5 and 33 ° C, a pressure of 0.955 bar and, in 32 stages. 22. System according to claim 13, characterized in that it comprises a separation step (b2) between ethylene (top of the column) and acetaldehyde (bottom of the column) (COLUMN2) in a temperature range between - 30 105 and 20 ° C, atmospheric pressure and, in 16 stages. 23. System according to claim 13, characterized in that it comprises a separation step (b3) between acetaldehyde (top of the column) Petition 870180140298, of 10/11/2018, p. 8/14 6/7 and ethyl acetate with water (column bottom) (COLUMN3) obtained in (b1) in the column bottom current (COLUMN1) in a temperature range between 20 and 70 ° C, an atmospheric pressure and, in 50 stages. 24. System according to claim 13, characterized by obtaining pure ethyl acetate (e1) comprising feeding a solvent, this ethylene glycol during separation (b3) between ethyl acetate (top of the column) and water with ethylene glycol (bottom) column) (COLUMN4) obtained in (b3) in the column top chain (COLUMN3) and, consequently, obtaining pure ethyl acetate, in a temperature range of 75 to 118 ° C, a pressure of 0.955 bar and, in 52 stages. 25. System according to claim 13, characterized in that it comprises a separation (b5) between water (top of the column) and ethylene glycol (bottom of the column) (COLUMN) obtained in (b4) in the chain at the bottom of the column (COLUMN4) in a temperature range between 98 and 195.5 ° C, a pressure of 0.955 bar and, in 22 stages. 26. System, according to claim 20, characterized by the ethylene glycol being recovered and recirculated, being able to feed again the separation phase of COLUMN 4. 27. Integrated production system for ethyl acetate, acetaldehyde, hydrogen, ethylene and water characterized by a β configuration comprising: (a) at least one fixed bed reaction medium with calcined hydrotalcite type catalyst; (b) at least five means for separating mixtures; (b1) separation means comprising at least one additional solvent stream; (c) means of exchange; (d) means of mixing solvents and reagents; (e) means for cleaning or activating the catalytic bed, cleaning the line, adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed; (f) means of separating the available hydrogen. Petition 870180140298, of 10/11/2018, p. 9/14 7/7 28. System according to claim 27, characterized in that it comprises at least one reaction medium, being this fixed bed multitubular reactor with calcined hydrotalcite catalyst; 29. System according to claim 27, characterized by 5 comprise at least five means for separating mixtures, these being distillation columns. A system according to claim 27, characterized in that it comprises separation means comprising at least one distiller fed with an additional solvent stream, this being ethylene glycol. 10 31. System according to claim 27, characterized by comprising indirect heat exchangers in counter-current between currents resulting from the process itself. 32. System according to claim 27, characterized by means of cleaning or activating catalytic bed, line cleaning, 15 adjusting the reaction temperature and monitoring the pressure drop in the catalytic bed, by feeding a nitrogen stream in element (a). 33. System according to claim 27, characterized by means of separating the available hydrogen, these being flash 20 or membrane reactor. 34. System according to claim 27, characterized in that said β configuration comprises a process according to claims 18 to 26.