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Pol. Con. (Edición núm. 63) Vol. 6, No 10Octubre 2021, pp. 673-692 ISSN: 2550 - 682XDOI: 10.23857/pc.v6i10.3232Análisis Técnico-Económico Para La Obtención De Etanol Celulósico A Partir De La Cáscara De ManíTechnical-Economic Analysis To Obtain Cellulosic Ethanol From Peanut ShellAnálise técnico-econômica para obtenção de etanol celulósico a partir de cascas de amendoimDiana Stefanía Cevallos-Álava I dcevallos0047@utm.edu.ec https://orcid.org/0000-0003-2978-6740Verónica Elizabeth Vinces-Álava II vvinces5798@utm.edu.ec https://orcid.org/0000-0001-9540-7337Ernesto Alonso Rosero-Delgado III ernesto.rosero@utm.edu.ec https://orcid.org/0000-0001-8878-8522Correspondencia: dcevallos0047@utm.edu.ecCiencias Técnicas y Aplicadas Artículo de investigación*Recibido: 30 de Agosto de 2021 *Aceptado: 22 de Septiembre de 2021 * Publicado: 26 de Octubre de 2021Facultad de Ciencias Físicas, Matemáticas y Químicas, Ing. Química, Universidad Técnica de Manabí, Portoviejo, Ecuador.Facultad de Ciencias Físicas, Matemáticas y Químicas, Ing. Química, Universidad Técnica de Manabí, Portoviejo, Ecuador.Facultad de Ciencias Físicas, Matemáticas y Químicas, Ing. Química, Universidad Técnica de Manabí, Portoviejo, Ecuador.http://polodelconocimiento.com/ojs/index.php/esResumenLa generación de energía convencional mediante combustibles fósiles conlleva generalmente al deterioro del medio ambiente. Por ello se buscan nuevas alternativas que compensen las necesidades del mundo actual. En la presente investigación se muestra un análisis técnico económico para la obtención de etanol celulósico a partir de hidrolizados obtenidos de cáscaras de maní tratadas con NaOH (3% m/v). Mediante un balance elemental se establecieron los coeficientes estequiométricos del proceso de fermentación de los hidrolizados. Se determinaron valores para el etanol YP/S= 0,44 gr gr-1 (%R= 85,35) y para las posibles emisiones YCO2/S= 0,43 gr gr-1. El perfil de alcoholes demostró la presencia de alcoholes superiores en el destilado final, en una concentración de 523,2 mg/100mL y de metanol 2128,1mg/100mL. Los indicadores económicos de un proceso industrial simulado, fueron: TIR 32,60% y un VAN positivo con un PRI de 4,74 años, el parámetro más susceptible durante el análisis de sensibilidad fue el costo de producción. La utilización de las cáscaras de maní muestra prometedores resultados en la producción de etanol de segunda generación, sin embargo, el uso industrial se ve condicionado a los procesos de hidrólisis y de destilación.Palabras claves: Alcoholes; fermentación; estequiometría; costo de producción; hidrólisis.AbstractConventional energy generation using fossil fuels generally leads to environmental deterioration. For this reason, new alternatives are being sought to compensate the needs of today's world. This research shows a technical-economic analysis for obtaining cellulosic ethanol from hydrolysates obtained from peanut shells treated with NaOH (3%). The stoichiometric coefficients of the hydrolysate’s fermentation process were established by means of an elemental balance. Values were determined for ethanol YP/S= 0,44 gr gr-1 (%R= 85,35) and for possible emissions YCO2/S= 0,43 gr gr-1. The alcohol profile showed the presence of higher alcohols in the final distillate, at a concentration of 523,2 mg/100mL and methanol 2128,1mg/100mL. The economic indicators of a simulated industrial process were: IRR 32,60% and a positive NPV with a PBP of 4,74 years, the most susceptible parameter during the sensitivity analysis was the production cost. The use of peanut shells shows promising results for production of second-generation ethanol; however, the industrial use is conditioned to the hydrolysis and distillation processes./9j/4AAQSkZJRgABAQEAYABgAAD/2wBDAAMCAgMCAgMDAwMEAwMEBQgFBQQEBQoHBwYIDAoMDAsK
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Diana Stefanía Cevallos Álava, Verónica Elizabeth Vinces Álava, Ernesto Alonso Rosero Delgado PAGE 692Pol. Con. (Edición núm. 63) Vol. 6, No 10, Octubre 2021, pp. 673-692, ISSN: 2550 - 682X PAGE 691Pol. Con. (Edición núm. 63) Vol. 6, No 10, Octubre 2021, pp. 673-692, ISSN: 2550 - 682XKey words: Alcohols; fermentation; stoichiometry; cost of production; hydrolysis.ResumoA geração de energia convencional a partir de combustíveis fósseis geralmente leva à deterioração do meio ambiente. Por isso, buscam-se novas alternativas para compensar as necessidades do mundo atual. Esta pesquisa apresenta uma análise técnica econômica para a obtenção de etanol celulósico a partir de hidrolisados obtidos de cascas de amendoim tratadas com NaOH (3% m / v). Por meio de um balanço elementar, foram estabelecidos os coeficientes estequiométricos do processo de fermentação dos hidrolisados. Os valores foram determinados para etanol YP / S = 0,44 gr gr-1 (% R = 85,35) e para emissões possíveis YCO2 / S = 0,43 gr gr-1. O perfil alcoólico evidenciou a presença de álcoois superiores no destilado final, na concentração de 523,2 mg / 100mL e 2128,1mg / 100mL de metanol. Os indicadores econômicos de um processo industrial simulado foram: TIR 32,60% e VPL positivo com PRI de 4,74 anos, sendo o parâmetro mais suscetível durante a análise de sensibilidade o custo de produção. O uso de casca de amendoim apresenta resultados promissores na produção de etanol de segunda geração, porém, o uso industrial está condicionado a processos de hidrólise e destilação.Palavras-chave: Álcoois; fermentação; estequiometria; custo de produção; hidrólise.IntroducciónLa rápida expansión de la población y el desarrollo industrial han llevado a un mayor consumo de combustibles fósiles (carbón, petróleo y gas natural) durante las últimas décadas. Los combustibles fósiles tienen una accesibilidad, compatibilidad y asequibilidad relativamente fácil (Wong, Lim et al. 2020), pero son recursos no renovables limitados que se consumen a un ritmo mucho mayor del que se produce.El bioetanol se produce básicamente a partir de cultivos alimentarios ricos en almidón y azúcar, que generalmente son obtenidos de cultivos alimentarios, lo que podría causar un desequilibrio en la cadena de suministro de alimentos y piensos (Kumar, Binod et al. 2018). Debido a estas preocupaciones relacionadas con la "compensación combustible-alimentos", así como las cuestiones ambientales y económicas que rodean biocombustibles convencionales, se handesarrollado numerosos estudios sobre el uso de biomasa como materia prima para la producción de etanol lignocelulósico. (Montico, S. 2016)Al utilizar biomasa la competencia de recursos en la producción de alimentos / combustibles podría mitigarse hasta cierto punto. Además, los nuevos conocimientos sobre el valor energético de los biocombustibles en comparación con los combustibles fósiles, generan preguntas sobre la eficiencia económica de los mismos. (Czekała, Bartnikowska et al. 2018).La agroindustria del Ecuador genera cerca de 2200 millones de kilogramos de residuos. (Riera, Maldonado et al. 2018). Por ello la producción de bioetanol de segunda generación es una alternativa futura, dado que los recursos agrícolas son abundantes en la naturaleza. Sin embargo, los estudios en esta área aún son limitados (Ventura Ríos, Honorato Salazar et al. 2017) ya que, a pesar de la alta disponibilidad y el bajo precio del material lignocelulósico, existe una fuerte resistencia a su degradación, lo que resulta en desafíos sustanciales en el uso de biomasa lignocelulósica.(Ning, Yang et al. 2021)En Ecuador existe la necesidad de actuar sobre desechos orgánicos como la cáscara de maní que todavía no tienen una disposición final adecuada ya que conlleva a prácticas poco amigables con el ambiente, debido a que se utilizan métodos como la quema del material a cielo abierto. (Muñoz & Robles 2019)En las últimas décadas se han realizado esfuerzos para desarrollar tecnologías eficientes y rentables que reduzcan el costo de producción de bioetanol. (Balan, Chiaramonti et al. 2013), sin embargo, la conversión de azúcares en etanol es desafiante, principalmente debido a la naturaleza resistente de la lignina a la degradación, la descomposición ineficaz de la celulosa y la hemicelulosa, la variedad de azúcares liberados de los polímeros de carbohidratos y el costo de almacenamiento, transporte, así como la recolección de materia prima lignocelulósica de baja densidad. (Almenares-Verdecía, Ngoma-Presline et al. 2011).Los caracteres químicos y estructurales de la lignina son las principales barreras para la conversión de biomasa en azúcares puesto que los polisacáridos están incrustados dentro de microfibrillas de celulosa ordenadas y compactas, incrustadas en una matriz de hemicelulosas y lignina (Zeng, Himmel et al. 2017), Lo cual dificulta el acceso del microrganismo a los azúcares para su conversión en etanol.Por otra parte, existen microorganismos capaces de fermentar monosacáridos (glucosa y fructosa) y disacáridos (maltosa y sacarosa) resultando en la producción de etanol y dióxido de carbono, sobre esto (López Toledo 2020) menciona que los principales azúcares para la producción de etanol de segunda generación son hexosas y pentosas (obtenidas de la biomasa lignocelulósica). Dentro de las ventajas del etanol lignocelulósico se menciona que posee un alto octanaje y una gran solubilidad en gasolina. Puede ser mezclado con gasolina en los vehículos convencionales, las mezclas de baja proporción de etanol anhidro (5%) no requieren adaptación alguna (Ascurra, Manosalva et al. 2019).Además de la disminución en las emisiones de CO2 (hasta un 70% menor comparado con la gasolina convencional, 90% en el caso de bioetanol de segunda generación), la adición de etanol a la gasolina permite reducir los niveles de SOx pues el etanol posee cantidades ínfimas de azufre comparado con el combustible fósil. (Serrano-Ruiz & Sotomayor 2011).Debido a la necesidad de conocimiento referente al uso de materias primas no convencionales generadas en procesos agro-productivos en el Ecuador, se estableció como objetivo del presente trabajo, la evaluación técnico-económica del proceso de producción de bioetanol de segunda generación, obtenido de la fermentación de hidrolizados generados del tratamiento básico de la cáscara de maní.Materiales y métodosEstandarización y pretratamientoSe utilizaron cáscaras de maní obtenidas de una peladora de la parroquia Lodana de la ciudad de Portoviejo-Ecuador, después se colectaron las cáscaras las cuales pasaron por un proceso de eliminación de impurezas y materiales particulados, posteriormente fueron sometidas a un secado a temperatura ambiente durante 24 h. La granulometría de las cáscaras fue estandarizada con la ayuda de un molino para granos manual y un tamiz (ø=1 mm) para los procesos de hidrólisis y posterior fermentación (Chauca Espinoza, Grosso Gamboa et al. 2017).Las cáscaras de maní después de su estandarización, se sometieron a hidrólisis básica. Para lo cual se tomaron 600 gr de cáscara de maní y se sumergieron en una solución de NaOH (3% m/v) y fueron sometidas a una temperatura de 121 °C con una presión de 0,15 MPa durante 1h en autoclave DAC-45 Human lab, según lo establecido por (Rodríguez, Castrillo et al. 2017). Unavez finalizada la hidrólisis, se filtró (ø=20µm) para separar la fase líquida de interés (hidrolizado), solución a la cual se le determinó la concentración de azúcares reductores (AzR gr/L solución).Determinación de azúcares reductoresLa determinación de azúcares reductores (AzR) se realizó por medio del método de DNS (Loboguerrero Avila 2007), para lo cual se ajustó el pH inicial del hidrolizado a 5 con HCl 1,09N. La reacción para evaluar los AzR se inicia cuando se agregan 0,5 mL del hidrolizado y 0,5 mL del reactivo de DNS, en tubos cónicos Falcón® de 15mL, dicha mezcla fue sometida a un baño termostático en una placa calefactora (Thermo) a 90 ºC durante un tiempo de 5 min. Los tubos Falcón® fueron enfriados a temperatura ambiente y se añadieron 5 mL de agua destilada, posteriormente se sometieron a agitación en una centrífuga (Pulsing Vortex Mixer, Fisher Scientific) para finalizar con la lectura en el espectrofotómetro a 540 nm (Thermo Scientific GENESYS 10S Spectrophotometers).FermentaciónLa fermentación se realizó por triplicado en biorreactores con una capacidad de 1L (75% volumen efectivo de hidrolizado), a los cuales se les ajustó el pH inicial a 5 (Castaño, Gordillo et al. 2020) con HCl 1,09N, posteriormente fueron inoculados con levadura comercial (Saccharomyces cerevisiae) a una concentración de 2,5% p/v (Muñoz, Ramírez et al. 2020). Estos biorreactores fueron sellados y conectados a una trampa que permitía la salida del CO2 producido en la reacción. La fermentación se llevó a cabo a una temperatura 25±5°C, durante un tiempo de 24 horas (Suárez-Machín, Garrido-Carralero et al. 2016). Finalizado el proceso de fermentación se evaluó la concentración de AzR final, valor que fue utilizado para calcular la cantidad de que fue consumida en el proceso de fermentación (Ec.1).%𝐴𝑧𝑅𝑐𝑜𝑛𝑠𝑢𝑚𝑖𝑑𝑎𝑠 = 𝐴𝑧𝑅𝑖𝑛𝑖𝑐𝑖𝑎𝑙 − 𝐴𝑧𝑅𝑓𝑖𝑛𝑎𝑙 (Ec.1)Por otra parte, teniendo en cuenta que la levadura S. cerevisiae no es capaz de utilizar pentosas para su crecimiento (Subtil & Boles 2011), se asume que el azúcar que se consume es la glucosa (C6H12O6), para el cálculo de este azúcar reductor se utiliza la (Ec. 2).%𝐺𝑙𝑢𝑐𝑜𝑠𝑎 = 𝐴𝑧𝑅𝑐𝑜𝑛𝑠𝑢𝑚𝑖𝑑𝑎 ∗ 100%(Ec. 2)𝐴𝑧𝑅𝑡𝑜𝑡𝑎𝑙𝑖𝑛𝑖𝑐𝑖𝑎𝑙Determinación de la cantidad de alcohol producidoSe determinó la cantidad de alcoholes superiores, furfural y metanol, así como la determinación del grado alcohólico. En el primer caso se utilizó el método de análisis PEE.LASA.FQ.45 INEN 2014 (determinación de productos congéneres por cromatografía de gases) y en el segundo el método PEE.LASA.BR.43 AOAC982.10. 2016 (por densitometría). Debido a que el alcohol absoluto expresa la suma de los alcoholes superiores, etanol y metanol, para determinar el volumen de etanol se aplicó la (Ec. 3).𝑉𝑒𝑡𝑎𝑛𝑜𝑙100𝑚𝑙 = 𝑉𝑎. 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑜 − 𝑉𝑚𝑒𝑡𝑎𝑛𝑜𝑙 − 𝑉𝑎. 𝑠𝑢𝑝𝑒𝑟𝑖𝑜𝑟𝑒𝑠 (Ec.3)Se determinó la concentración porcentual de etanol relacionando el volumen de etanol y el volumen de alcohol absoluto mediante la (Ec. 4).%𝐸𝑡𝑎𝑛𝑜𝑙 =𝑉𝑒𝑡𝑎𝑛𝑜𝑙𝑉𝑎.𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑜∗ 100 (Ec.4)Estequiometría del proceso de producción de bioetanolSe realizó un balance estequiométrico y macroscópico para determinar los coeficientes de rendimiento del proceso fermentativo (YX/S, YP/S, YCO2/S.) y demás indicadores biológicos que permitan evaluar el rendimiento del proceso de producción de bioetanol de segunda generación a partir de cáscara de maní. Para todo el proceso de cálculo se utilizó la metodología descrita por Doran (2012), basada en la ecuación estequiométrica del proceso de fermentación de células heterótrofas. (Ec. 5).𝐶𝑤𝐻𝑥𝑂𝑦𝑁𝑧 + 𝑏𝑁𝐻𝑖 → 𝑐𝐶𝐻𝛼𝑂𝛽𝑁𝛿 + 𝑑𝐶𝑂2 + 𝑒𝐻2𝑂 + 𝑓𝐶𝑗𝐻𝑘𝑂𝑙𝑁𝑚 (Ec.5)En donde: CwHxOyNz representa al sustrato, NHi la Fuente de Nitrógeno, CHαOβNδ la biomasa generada y CjHkOlNm el producto obtenido.Para la determinación de los coeficientes máximos termodinámicos se tomó en cuenta la fracción de electrones disponibles transferidos al producto, en este caso el bioetanol en ausencia de síntesis de biomasa y del sustrato al O2 para el rendimiento de biomasa, mediante la siguiente ecuación.𝐶𝑚á𝑥= 𝜔𝑦𝑠𝑦𝑏𝑚𝑜𝑙𝑠𝑢𝑠𝑡𝑟𝑎𝑡𝑜(Ec.6)()𝑚𝑜𝑙𝑏𝑖𝑜𝑚𝑎𝑠𝑎() (Ec.7)𝐹= 𝜔𝑦𝑠 𝑚𝑜𝑙𝑠𝑢𝑠𝑡𝑟𝑎𝑡𝑜𝑚á𝑥𝑗𝑦𝑝𝑚𝑜𝑙𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑜En donde: yp, yb y ys representan la cantidad de electrones disponibles para producto, biomasa y sustrato respectivamente. El número de carbonos en el sustrato y el producto expresados como ω y j. Los rendimientos máximos termodinámicos se expresan en unidades de masa (gr) para su comparación con el rendimiento experimental.Evaluación EconómicaCostos de capital de operación de índices económicos.Para la evaluación económica se propuso la capacidad de procesamiento de 1000 Litros de etanol/día (781,11 kg/día) con el objetivo de determinar su viabilidad. La evaluación económica fue realizada siguiendo la metodología descrita por Peters, Timmerhaus et al. (1991). Los indicadores económicos valor actual neto (VAN), tasa interna de retorno (TIR) y plazo de recuperación de inversión (PRI), fueron calculados con los datos establecidos en relación a costos de inversión y producción, basados en los resultados obtenidos durante la experimentación. Además, se realizó un análisis de sensibilidad considerando variables que influyen directamente en la rentabilidad del proyecto.Resultados y DiscusiónHidrólisis.Del proceso de hidrólisis de la cáscara de maní se establece que la concentración de la solución de NaOH (3%) necesaria para hidrolizar la cáscara de maní es de 2,5 mL por cada gramo de material, siendo esta la cantidad necesaria para que la solución (NaOH) reaccione en el proceso y así evitar costos innecesarios. En la Tabla 1 se observan los resultados de este ensayo, en donde se demuestra que no existe una diferencia en cuanto a la concentración de AzR finales al disminuir el volumen de solución utilizada para la hidrólisis.Tabla 1. Efecto de la relación volumen de la solución de NaOH/gramos de cáscara de maní en la concentración de azúcares reductores.Cáscara de maní(gr)NaOH(mL/gr)AzR Final(gr/L)10,015,06,16±0,210,07,56,21±0,110,02,56,18±0,1En la Tabla 2 se presentan los resultados del contenido de azúcar antes y después del proceso de fermentación, con estos datos se determinó el valor de la glucosa consumida durante este proceso (28%), se asume que el proceso de hidrólisis genera glucosa como azúcar reductor, debido a que los hidrolizados de biomasa vegetal típicamente contienen mezclas de azúcares como D-glucosa y D-xilosa y de L-arabinosa. (Subtil, T & Boles, E, 2011) (Wang, Chan et al. 2020).Tabla 2. Concentración de azúcares reductores antes y después del proceso de fermentación.AzR Inicial (gr)AzR Final (gr)Glucosa consumida0,0927 ± 0,030,0668 ± 0,020,026 (gr)28,00 %Balance estequiométrico del proceso de fermentaciónEn la (Ec.8) se muestran los compuestos involucrados en la obtención de bioetanol con sus respectivos coeficientes estequiométricos y en la Tabla 3 los rendimientos estequiométricos alcanzados en el proceso.𝐶6𝐻12𝑂6 + 0,015𝑁𝐻3 → 0,75𝐶1𝐻1,83𝑂0,56𝑁0,02 + 1,83𝐶𝑂2 + 0,21𝐻2𝑂 + 1,71𝐶2𝐻6𝑂1 (Ec.8)*Los coeficientes de la ecuación estequiométrica están expresados en unidades de moles.Tabla 3. Rendimientos estequiométricos.Ygr NH3/ gr SYgr X/ gr SYgr CO2/ gr SYgr H2O/ gr SYgr C2H6O1/ gr SYgr C2H6O1/ gr S(Max)R(%)0,020,110,430,040,440,5185,35El rendimiento del producto (YP/S), encontrado en esta investigación fue de 0,44 gr C2H6O1/gr C6H12O6 valor cercano al rendimiento máximo termodinámico (YP/Smax) que se puede alcanzar, el cual es 0,51 gr C2H6O1/gr C6H12O6.Por otra parte, el rendimiento YP/S, obtenido en esta investigación es mayor al informado por (Akpan, Kovo et al. 2005) quienes reportan un valor de 0,23 gr C2H6O1/gr C6H12O6 utilizando el mismo residual. Hay que tener en cuenta que los autores en mención, usaron un cultivo mixto de B. stearothermophilus y S. cerevisiae, además, emplearon una concentración de cultivo de 2%p/v menor al reportado en la presente investigación. Lo cual pudo haber afectado al rendimiento final ya que posiblemente no se aprovecharon todos los azúcares, además el microorganismo usado para el cultivo mixto podría no se ser el adecuado para éste proceso, posiblemente inhibiendo la actividad de la levadura puesto que generalmente se usa B. stearothermophilusse en cultivos puros (Dutta,2008).Así mismo en un estudio realizado por (Beltrán-Arredondo, Hernández-Leyva et al. 2020) se obtuvo bioetanol a partir de rastrojos de maíz en donde se aislaron y seleccionaron levaduras de residuos agroindustriales obteniéndose un YP/S = 0,31 gr C6H12O6/gr AzR, valor diferente al de esta investigación, esto puede deberse a que estos autores usaron un pretratamiento ácido.(Mukherjee, G et al. 2017) mencionan que para residuos lignocelulósicos el pretratamiento alcalino es el indicado debido a que provoca hinchazón de la celulosa, reduciendo así su cristalinidad, lo que se traduce en un mayor rendimiento de azucares reductores. Por otro lado, el rendimiento obtenido en esta investigación es menor que el estudio reportado por (Santi, Jasiulewicz et al. 2015) quienes utilizaron cáscara de naranja como sustrato, sin embargo, estos autores utilizaron explosión de vapor catalizada por ácido, sacarificación enzimática y fermentación simultánea en el proceso, con lo cual alcanzaron un valor de YP/S = 0,49 gr C2H6O1 /gr AzR , por lo que queda en evidencia que la aplicación de técnicas más agresivas en la hidrólisis mejoran la productividad y el rendimiento final.En la fermentación los azúcares liberados durante la hidrólisis son fermentados produciéndose etanol y CO2, en esta investigación el coeficiente para el CO2 fue 0,43 gr CO2/ gr C6H12O6 ya que al ser una levadura comercial específica para otros procesos probablemente tenga influencia en la producción de CO2. Por otro lado, para el caso de la biomasa se obtuvo un coeficiente de 0,11 gr gr-1 C6H12O6, valor que coincide con el reportado por (Zapata, J., Hoyos, M., & Quinchía, L. A. 2005) en donde se evaluó el crecimiento de Saccharomyces cerevisiae en melaza. Según lo mencionado por (Vázquez & Dacosta 2007) las cantidades de CO2 y biomasas producidas se deben a que las levaduras derivan cierta parte de la fuente de carbono hacia otras funciones como el mantenimiento celular y el crecimiento, por lo que en la práctica es muy difícil obtener conversiones altas de etanol.Producción industrial (1000 L de bioetanol).En la Tabla 4 se presenta un balance de masa en el que partiendo de la cantidad de azúcares totales fue posible calcular la cantidad de insumos para la obtención de 1000L de etanol.Tabla 4. Balance de masa de la producción de bioetanol.Corrientes (kg/lote)Entrada (kg)Genera (kg)Salida (kg)Cáscara de maní3000,97-3000,97Solución de NaOH7130,88-2928,90Levadura10,72--Vinaza-3180,633180,63Etanol-781,11781,11Furfural-68,7668,76Alcoholes superiores Metanol--35,76146,4435,76146,44Flujo total10142,48-10142,48Como se puede observar la cantidad de insumos necesarios es considerable, sin embargo, hay que recalcar que la materia prima empleada es un residuo, lo cual generalmente no tiene muchas aplicaciones ya que su uso principal es como abono para la tierra, comida para ganado y una gran parte de ésta es quemada al aire libre (Muñoz & Robles 2019) ,lo cual contribuye efectos sobre el medio ambiente. La utilización de la cáscara evitaría su quema y el uso de más extensiones de tierra para plantar caña de azúcar.Después del proceso de fermentación de los hidrolizados de la cáscara de maní, se obtienen subproductos de gran interés como vinazas, metanol, furfural y alcoholes superiores que podrían ser aprovechados y ofertados a las industrias generando así más ingresos, el subproducto generado en mayor volumen en el proceso, fueron las vinazas con una cantidad de 3180,63 kg, efluente que podría ser tratado con una digestión anaerobia y ser empleado en la producción de biogás como alternativa para disminuir los gastos fijos de la planta(Lorenzo-Acosta, Doménech-López et al. 2015).Perfil de alcoholes.En la Tabla 5 se presentan las concentraciones obtenidas de los ensayos de determinación de alcoholes y furfural por cada 100 ml de alcohol absoluto.Tabla 5. Resultados de determinación de la concentración de alcoholes y furfural en el destilado.ParámetrosConcentración (mg/100mL)Alcoholes superiores523,2Furfural1,0Grado alcohólico a 20oC0,1 Metanol2128,1El análisis químico del destilado final demuestra la presencia de alcoholes superiores en una concentración de 523,2 mg por cada 100mL de alcohol absoluto. (Loviso & Libkind 2019) mencionan que los alcoholes superiores pueden producirse por dos vías, la vía de Ehrlich para el catabolismo de aminoácidos y la vía de Harris para el metabolismo del azúcar. Es así que cuando la cantidad de nitrógeno es suficiente, los aminoácidos se transforman en alcoholes superiores mediante una secuencia de reacciones, entonces, Saccharomyces cerevisiae, microorganismo utilizado en este estudio no es capaz de utilizar todas las sustancias nitrogenadas para el crecimiento y el metabolismo por lo que parte del nitrógeno no es consumido por la levadura (Zhong, Wang et al. 2020). Se conoce que, en la última etapa de la fermentación, la fuente de nitrógeno está casi agotada, lo que conduce a la relativa falta de nitrógeno durante la fermentación. En estas condiciones, la fuente de carbono es relativamente abundante, y las células se someten a la vía de síntesis bioquímica (metabolismo de Harris), produciendo el 75% de los alcoholes superiores (Zhang, Liu et al. 2016).Así mismo se encontró un valor de furfural de 1,0 mg por cada 100mL de alcohol absoluto. (Rosales-Calderón & Arantes 2019) Mencionan que la fermentación puede ser inhibida por varios compuestos y estos pueden estar presentes de forma natural en la biomasa o formarse durante el pretratamiento, conteniendo furfural, por lo que se asume que su formación se debe a cambios bruscos de temperatura y pH, tal como sucede en la presente investigación.La concentración de metanol en el producto destilado fue de 2128,1mg por cada 100mL alcohol absoluto, la presencia de metanol puede deberse según varios autores a dos factores principales: La cepa utilizada y las condiciones de fermentación (Temperatura, aireación y características del residuo.) en ésta investigación la fermentación se desarrolló a temperatura ambiente (25±5°C), dicha condición pudo ser un factor determinante en la formación de metanol efecto que podría evitarse manteniendo la temperatura cercana al valor óptimo para el microorganismo (33 a 34°C). (Suárez-Machín, Garrido-Carralero et al. 2016).Por otra parte, estudios recientes también han demostrado que existen cepas Saccharomyces cerevisiae con un metabolismo ligeramente diferente, las cuales pueden derivar en la producción de metanol. Además, (Ohimain 2016) menciona que la falta de técnicas adecuadas de fermentación y destilación puede ser un factor clave que contribuye al alto contenido de metanol en los productos.El valor obtenido de etanol fue de 0,097 mL C2H6O1 /100mL de muestra, que corresponde al 85,35% lo que comprueba que es posible obtener este producto a partir de la cáscara de maní y, por otro lado, que la levadura S. cerevisiae es capaz de aprovechar los azúcares reductores generados en el proceso hidrolítico de estos materiales.En la investigación realizada por (Márcio Santos Cabral, Karla de Souza Abud et al. 2016) obtuvieron una eficiencia de conversión de etanol de 59,60% a partir de fibra de coco verde, rendimiento bajo, el cual podría deberse a que el contenido de lignina antes del tratamiento alcalino de dicho residuo es 40,10% mientras que el del residuo utilizado en la presente investigación es del 33,00% aproximadamente, lo cual podría ser un punto clave en el rendimiento YP/S. Algo similar ocurre en la investigación de (Li, Shen et al. 2016) quienes mediante una cepa modificada de S. cerevisiae alcanzaron rendimientos de etanol mayores al 80,00% se menciona que estas cepas exhibieron el uso de la xilosa como sustrato además de la glucosa.Teniendo en cuenta algunos resultados mostrados se debe resaltar que con técnicas más sencillas y de menor costo como en el caso de la presente investigación, se pueden lograr rendimientos considerablemente competitivos, sin embargo, sigue siendo un aspecto clave el consumo de otros azúcares adicionales a la glucosa.Análisis económicoComo se muestra en la Tabla 6 el precio obtenido por galón de etanol celulósico resultó de$2,29/galón, se podría considerar favorable puesto que según el Laboratorio Nacional de EnergíaRenovable (Bioenergy) en el año 2012 expusieron que el etanol celulósico comercial puede tener un costo aproximado de $2,15 el galón, valor cercano al obtenido en el presente estudio, cabe mencionar que el costo obtenido en esta investigación podría disminuir si se utilizan insumos a un nivel industrial.Tabla 6. Indicadores económicos de la producción de 1000 L de etanol de segunda generación a partir de cáscara de maní.InversiónCosto (galón)TIRPRI $ 180092,60$2,2932,60%4,74 añosEl alto costo de los productos obtenidos por procesos biológicos, se debe a una combinación de precios de materias primas y requisitos de procesamiento extensos, particularmente como en este caso para materias primas lignocelulósicas. (Tobin, Gustafson et al. 2020). En un estudio realizado por (Herring, Narayanan et al. 2016) informan que generalmente los precios por galón de bioetanol (escala industrial) obtenidos a partir de residuos de pericarpio de maíz y cáscara de maní, pretratados con peróxido de hidrógeno y sacarificación simultánea son de $2,39 y $2,32 respectivamente.En la Tabla 6 se observa que el plazo de recuperación del capital invertido es de 4,74 años dicho tiempo es considerado de riesgo normal ya que es menor que 5 de acuerdo al criterio de (Allaire & Cunningham 1980), es decir se prevé la recuperación de la inversión inicial en un tiempo adecuado. La TIR de la presente investigación se considera aceptable (Ibáñez Bustos, Soto González et al. 2018) ya que tiene un valor de 32,60% lo cual nos indica que el proyecto devuelve el capital invertido más un adicional por lo que el proyecto sería rentable.Cabe recalcar que lo que se presenta es una evaluación teórica, cuyos valores son obtenidos a partir del monitoreo del costo de los insumos en el mercado, considerando que la técnica usada en la producción de bioetanol con cáscara de maní está aún en desarrollo, y estos podrían mejorar realizándose estudios en cuanto a los subproductos que se obtienen para aprovechar así la totalidad del proceso, disminuyendo los costos.Análisis de sensibilidad.En la Figura 1 se puede observar cómo se afecta la variación de la TIR de una manera gráfica, según el porcentaje de variación de los diferentes escenarios.TIRiVBORw0KGgoAAAANSUhEUgAAAc8AAAF+CAYAAADk7pH7AAAABmJLR0QA/wD/AP+gvaeTAAAACXBI
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60%50%40%MATERIA PRIMA30%20%COSTO DE PRODUCCIÓNCOSTO DE INVERSIÓN RENDIMIENTO DE PRODUCTO VOLUMEN DE HIDROLIZADO10%0%-30%-20%-10%0%10%20%30%HIPÓTESIS DE BASEFigura 1. Análisis de sensibilidad.Se presenta una pendiente más evidente con el parámetro que es más sensible a las variaciones, en este caso el costo de producción, por otro lado, el costo de inversión, materia prima, rendimiento de producto y volumen de hidrolizado muestran una pendiente con menor inclinación, lo cual indica que estas variables influyen en menor medida la rentabilidad del proyecto.Entre las variables más influyentes del proceso se tienen la materia prima, los costos de producción, de inversión, volumen de hidrolizado y rendimiento de producto. Indicadores tales como volumen de producción, ingresos por ventas, costos de inversión y costos de materias primas y materiales requieren ser examinados con una mayor precisión, ya que sus valores están sujetos a mayores variaciones. (Ramírez et al., 2009).La materia prima está relacionada directamente con los costos de producción, que a pesar de su bajo precio conlleva el uso de insumos para su pretratamiento, afectando al precio final de producto.Se consideró el costo de inversión debido a los rubros de las maquinarias, ya que para el proceso se requieren varios equipos de grandes dimensiones para las diferentes operaciones, sin embargo, ésta no presenta variaciones exageradas en el estudio de los escenarios, al mismo tiempo se tomó en cuenta la variable del volumen de hidrolizado debido a que se relaciona con la concentraciónde azúcares reductores, es decir entre más líquido se obtenga mayor es la cantidad para fermentar, lo cual es favorable porque las levaduras pueden aprovechar la mayor parte de azúcares reductores del residuo pretratado durante la fermentación, y esto se refleja directamente en el rendimiento de producto.En cuanto al rendimiento de etanol indica la cantidad de producto por cantidad de sustrato consumido, es decir, entre mayor sea la transformación de glucosa en etanol la rentabilidad incrementa, porque la cantidad de etanol aumentará y se relaciona directamente con el costo de producción.Según el análisis de sensibilidad el costo de producción es el aspecto que más afecta a los indicadores económicos siendo así que al aumentar un 10% de éste se reduce la TIR a un 21%, es decir el proyecto disminuiría considerablemente su rentabilidad, ya que la inversión se recupera en un tiempo no adecuado (6,40 años), los elementos considerados en el costo de producción se muestran en la Tabla 7.Tabla 7. Elementos del costo de producción de etanol de segunda generación obtenido de la cáscara de maníElementos del costo de producción$/año%Directos173.027,95Materias primas120.124,6555,0Salarios vinculados al proceso productivo43.240,3219,8Facilidades auxiliares1.978,950,9Mantenimiento3.054,551,4Suministros de operación305,450,1Laboratorio4.324,032,0Indirectos2.138,18Impuestos1.527,270,7Seguro social610,910,3Depreciación2.958,401,4Gastos generales23.147,4310,6Administrativos17.296,137,9Total218.568,1100ConclusionesLos resultados obtenidos en esta investigación mostraron que los azúcares están contenidos en una medida razonable en la cáscara de maní y mediante un proceso de fermentación conSaccharomyces cerevisiae es posible obtener etanol de segunda generación, sin embargo, también se obtienen otros compuestos como furfural, metanol y alcoholes superiores, que podrían ser de interés como materia prima para otros procesos. Luego de la fermentación se logró obtener un rendimiento de producto de 0,44 gr/gr, considerándose alto puesto que el máximo termodinámico (teórico calculado) es 0,51 gr/gr, por otra parte, los coeficientes para el CO2 y H2O fueron de 0,43 gr/gr y 0,04 gr/gr respectivamente, valores considerablemente altos, lo que indica que es importante considerar el uso de una cepa de S. cerevisiae específica para la producción de etanol. El análisis económico demuestra que el proyecto se presenta favorable con una TIR de 32,60% la cual se considera aceptable, ya que devuelve el capital invertido en un plazo de 4,74 años (PRI). El análisis de sensibilidad demuestra que el parámetro que más influye es el costo de producción. 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