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Dehydration of Ethanol by PSA Process with Pressure Equalization Step Added

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Dehydration of Ethanol by PSA Process with Pressure Equalization Step Added Bioethanol 2016; 2: 76–83 Research Article Open Access Luz Elena Gomar-Madriz, Jaime Saucedo Luna, Medardo Serna-González, Salvador Hernández-Castro, Agustin Jaime Castro-Montoya* Dehydration of Ethanol by PSA Process with Pressure Equalization Step Added DOI 10.1515/bioeth-2016-0004 Received December 16, 2014; accepted March 31, 2015 1 Introduction Abstract: In this work, the ethanol dehydration production Currently, a major concern worldwide is the declining process is carried out using the Mathematical Modeling of fossil energy reserves and the environmental impact Pressure Adsorption Process. A new model is suggested, it has that its use has caused, thus, research and development two equalization steps, and is compared with the Industrial of renewable energy sources have intensified in the last Pressure Swing Process operating cycle. An analysis of years. As transport is the main generator of greenhouse the effects of introducing the pressure equalization step gases, a great effort has been directed towards producing is performed on four main response variables: purity, biofuels, being ethanol the most promising alternative to be production, recovery and energy consumption and it is used as an additive or substitute for gasoline. Nowadays, compared with the current cycle configuration operating in ethanol is produced through several processes such as the industry. We used Aspen Adsorption for the valuation sugar-based raw materials (e.g. sugar cane), starch-based and simulation of the cyclic PSA process. We analyzed and raw materials (e.g. corn) and biomass-based raw materials processed the simulation results in Statgraphics Centurion (e.g. agricultural residues such as corn stover and wheat to obtain optimum operating conditions for the process. straw). These technological processes are different from This evaluation shows that purity decreases slightly, one another in their initial phase, but something they have whereas recovery and production increase. The most in common is that they produce very diluted ethanol (6-10% important thing is that the energy consumption is reduced. wt), which needs to be dehydrated for use it as a gasoline These results clearly show that by modifying the operating additive. An ethanol-water mixture forms a minimum- cycle schema, optimum operating conditions also change. boiling azeotrope ethanol composition of 95.6% wt at an The optimization of the new cycle was executed considering atmospheric pressure of 78.15°C, limiting its dehydration as variables bed pressure, adsorption time and purging by conventional distillation. As a result, a great deal of flow. We found that a smaller column is more productive alternatives have been reported to produce anhydrous for the equalization cycle than that of a 14m bed, which is ethanol through azeotropic distillation, extractive optimal in the industrial cycle with a consequent reduction distillation, vacuum distillation, extractive distillation in adsorbent material. with salt effect, pervaporation and adsorption [1-5]. The most common within the industrial scale is the extractive Keywords: Ethanol Anhydrous, Pressure Swing distillation with a solvent, but it is high energy-consuming. Adsorption, Pressure Equalization PSA process was developed in the 1960s [6] and it was initially used as a technique to separate air particles, produce oxygen and nitrogen or to remove impurities from *Corresponding author: Agustin Jaime Castro-Montoya, Facultad gases. In recent years, the interest in PSA has increased due de Ingeniería Química, Universidad Michoacana de San Nicolás de Hidalgo, Francisco J. Mújica S/N, Ciudad Universitaria, 58060 Morelia, to its low-energy consumption levels [7], and it has been Mich., México; E-mail: [email protected] used in the bioethanol industry. Skarstrom’s cycle operates Luz Elena Gomar-Madriz, Jaime Saucedo Luna, Medardo Serna-Gon- in two beds and each bed operates in two phases with similar zález, Facultad de Ingeniería Química, Universidad Michoacana de time periods. The first phase is pressurization followed San Nicolás de Hidalgo, Francisco J. Mújica S/N, Ciudad Universita- by adsorption, and the second one is depressurization ria, 58060 Morelia, Mich., México Salvador Hernández-Castro, DCNyE, Departamento de Ingeniería followed by purge. Pressurization is carried out in the Química, Universidad de Guanajuato, Noria Alta S/N 36050, Guana- feeding step, while a portion of the produced flow is used juato, Gto., México to purge the bed. Since Skarstrom’s cycle was introduced, © 2016 Luz Elena Gomar-Madriz et al., published by De Gruyter Open. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License. Dehydration of Ethanol by PSA Process with Pressure Equalization Step Added 77 there have been a number of modifications aimed at state approach in Aspen Adsorption software. The increasing the purity of the produced gas, product recovery, mathematical equations used are summarized in Table 1 the production of the adsorbent and energy efficiency [8]. and are based on the following approximations: Among the best improvements that have been introduced is – An ideal gas is considered. the incorporation of a pressure equalization step typically – The radial dispersion is negligible. after the first bed is purged and the second bed has – The bed operates under non-isothermal and non- completed the adsorption step under high pressure. Rather adiabatic processes and the gas, the solid and the than starting with the draining of the second bed, both beds bed’s wall have thermal conductivity. are connected to an equal pressure. Thus, the first bed is – The velocity of the superficial gas is related to the partially pressurized while the second bed is depressurized pressure gradient according to the Ergun equation. to equalize the pressure. At the end of the equalization – Primary resistance to mass transfer is combined into a phase, the second bed continues to be depressurized and single grouped parameter, where the driving force is a purged, while the first bed is being pressurized [9]. Actually, linear function of the weight of the solid. commercial scale processes operate in a two-column cycle, – Adsorption equilibrium is well-described by the which includes an adsorption or production step in which Langmuir Adsorption Isotherm Model. vapor-feed is supplied at 167°C, at a pressure of 379.2 kPa and at a concentration of between 92% wt and 93% wt of ethanol, in order to get a product with a 99% wt ethanol 2.2 PSA process design alternatives purity within a 345 s time cycle. A portion of the product is taken to purge for 15 s, and the 2nd bed is pressurized The two PSA alternatives are developed in Aspen during 120 s. The desorption step is divided into several Adsorption. The first alternative studies the setting cycle sub-stages: i) First, depressurization pressure decreases for water adsorption in zeolite to dehydrate ethanol that from 379.2 kPa to 137.9 kPa at only 60s to create a vacuum in is used in the industry [14] with the operation parameters counter-current; ii) Second, the depressurization where the reported in Table 2. The schematic design of this process pressure is lowered from 137.9 kPa to 37.9 kPa at 150 s; iii) is shown in Figure 1. It has 4 stages, which are described Third, purging at 37.9 kPa for 15s with produced anhydrous as follows [15]. It is noteworthy that while the bed 1 is in ethanol; iv) Pressurization during 120 s of the second bed the adsorption step (I), the bed 2 performs the other three to provide a portion of the effluent produced in bed 1 [2, stages: depressurization (II), purge (III) and pressurization 10-13]. Introducing a pressure equalization step in other (IV). When the cycle is complete, the sequence of steps is processes such as hydrogen purification has shown an exchanged in the beds. This applies also to the proposed improved process performance [7]. new cycle. In this research work, the ethanol dehydration I. Adsorption: A 700 kmol/h ethanol aqueous solution production process analysis is carried out using the at 92.5% wt is fed during 345 s and operated under an Mathematical Modeling of Pressure Swing Adsorption adsorption pressure of 379.2 kPa at a temperature of (PSA). An analysis of the effects of introducing the pressure 125°C. During this stage, a 100 kmol/h product sample equalization step is performed on four main response is taken to purge the bed for 15 s and 525 kmol/h to variables: purity, production, recovery and energy pressurize it for 120 s. consumption and it is compared with the current cycle II. Depressurization: This is done in two stages. The first configuration operating in the industry. Aspen Adsorption stage is a linear depressurization done in 60 s, which was used for the valuation and simulation of the cyclic allows the scheme to reach a pressure of 137.9 kPa. PSA process. The simulation results were analyzed and The second stage is an exponential depressurization processed in Statgraphics Centurion to obtain optimum done in 150 s, reaching a pressure of 13.8 kPa. operating conditions for the process. III. Purge: Maintaining vacuum pressure at 13.8 kPa, the system is purged with a 100 kmol/h sample taken from anhydrous ethanol produced during 15 s. 2 Material and methods IV. Pressurization: For 120 s, 525 kmol/h of anhydrous product is taken to pressurize the bed from 13.8 kPa 2.1 Mathematical modeling to 379.2 kPa. Simulation of the industrial cycle and the pressure The process operates in two beds; both beds have the equalization step cycle is carried out under a steady- same characteristics and are presented experimental 78 L.E. Gomar-Madriz, et al. Table 1. Mathematical adsorbent bed model used for Aspen Adsorption. equilibrium data [16]. Also using the Clausius-Clapeyron and in a concentration of 92.5% wt, with a flow of equation, water adsorption heat and ethanol were 700 kmol/hr.
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