Bioenergy and Industrial Applications of Grape Pomace from “Vinho Verde”
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Ourania Klapa Bioenergy and industrial applications of grape pomace from “Vinho Verde” Bioenergia e aplicações industriais do bagaço de uva do "Vinho Verde" Mestrado em Sistemas de Energias Renováveis Master in Renewable Energy Systems Dissertation / Biomass Coordinator: Professor Preciosa Pires Co-coordinator: Professor Mário Barros November 2015 I II Bioenergy and industrial applications of grape pomace from “Vinho Verde” Constitution of jury: Maria Gabriela Coutinho Soares Lema Botelho, PhD Assistant Professor Area of chemistry University of Minho (External jury) Preciosa de Jesus da Costa Pires, PhD Professor Coordinator Area of chemistry Escola Superior de Tecnologia e Gestão do Instituto Politécnico de Viana do Castelo [ESTG-IPVC] (Orientator) Paulo Jorge Campos Costa, PhD Associate Professor Area of Electronics and Automation / Renewable Energy Escola Superior de Tecnologia e Gestão do Instituto Politécnico de Viana do Castelo [ESTG-IPVC] (Chairman) III IV Bioenergy and industrial applications of grape pomace from “Vinho Verde” “The secret of change is to focus all of your energy not on fighting the old, but on building the new” Socrates V VI Bioenergy and industrial applications of grape pomace from “Vinho Verde” Acknowledgments This research took place in the period 2014-2015 and was held at the Chemistry Laboratory, IDEALQ in Escola Superior de Tecnologia e Gestão (ESTG) of Instituto Politécnico de Viana do Castelo (IPVC), which I feel greatly thankful for their immediate acceptance. I would like to dedicate my sincere thanks to my major adviser Mrs. Preciosa Pires for the confidence she showed me, the continuous availability, the factual support and guidance and for the excellent cooperation and friendly disposition with the human contact that we have developed. I appreciate Mr. Mário Barros being my co-coordinator and participating in my master program, helping with the statistics used in this thesis. Especially, I would like to recognize Mrs. Elia Fernandes for her professional guidance on laboratory analyses and suggestions in the experimental part of the work, for creating a pleasant and warm working environment and for every kind of support and help she offered me, the sympathy and her friendship. I dedicate many thanks to Mrs. Luisa Imperadeiro for performing all the necessary laboratory procedures for completion of my research, for the support and for the excellent cooperation we had in the lab. I dedicate many thanks to Mr. Augusto Gil for helping me in the economic study that was made in this research, to the technicians from Unidade de Investigação, Desenvolvimento e Inovação em Ciência e Tecnologia Alimentar (UIDICTA), for providing some equipment and to Mr. Nuno Vitorino for the availability and help. I deeply acknowledge my family and my friends in Greece for unconditionally supporting me to come to Portugal and pursue my master studies. Their love always follows me wherever I am and encourages me to fulfill my goal. Last but not the least, I thank Michael who make my life more than just research and gives me physical and mental supports continuously. I sincerely acknowledge for all those, I did not mention explicitly, who have helped me in these two years. I would like to state my obligation towards Adega Cooperativa de Ponte da Barca for donating GP and to Centro de Estudos Ibéricos (CEI) for funding the present thesis. VII VIII Bioenergy and industrial applications of grape pomace from “Vinho Verde” Abstract Portugal is the fifth largest wine producer in the EU-28 and eleventh in the world, with a wine production estimated at 5,886 khL in 2014. In this year, the Portuguese Minho region had a production over 530 khl of “Vinho Verde” wine. Grape pomace (GP) is an agro- industrial residue from this process, consists of stalks, skins and seeds, and accounts for about 20-25% weight of the grape crushed for the wine production. Ιn Minho region almost 18x103 tons of GP are generated, which are mainly employed for animal feed, fertilizer or depositing in the οpen fields and can cause environmental problems. The uncontrolled dumping of these by-products causes phytotoxicity phenomena and contributes to the green house gas emissions. The objective of this study was to evaluate the potential application of grape pomace, from Vinhão and Loureiro grape varieties, as bioenergy or as raw material in other industrial processes. Analyses were made in one white and one red GP variety, named Loureiro and Vinhão, respectively, from Adega Cooperativa de Ponte da Barca. The chemical properties studied were moisture, ash, Kjeldahl N, fat, carbohydrates, fiber, minerals, total phenolic content (TPC), antioxidant activity, and identification/quantification of nine polyphenols applying standard methods of analysis. The high heating value (HHV) was determined by the method from Parr instruments. The moisture in GP varies from 42.2% to 72.8%. Results in dry matter show that the contents are 3.3% to 7.9% in ash, 1.0% to 2.1% in Kjeldahl N, 2.0% to 16.4% in fat, 15.4% to 29.2% in carbohydrates, 11.9% to 31.0% in fiber, 23.9 to 120 mg GAE/g for TPC and 12.2 to 83 mg AAE/g for antioxidant activity. Comparing the two varieties of GP for the polyphenols, Vinhão has a higher content than Loureiro in eight identified polyphenols, except for resveratrol, which is higher in the Loureiro stalks (0.244 mg/g DM) and is close to the highest value in literature. The HHV of GP before and after extracting the bioactive products is between 17-21 MJ/Kg, which compares to the best hardwood biomass. Considering the results obtained, GP is a very valuable raw material with potential to be used in industrial processes in a profitable way. The process should start with the bioactive extractions, followed by the production of grape seed oil and grape flour for human nutrition and cosmetology. Finally, the remaining stalks could be used as fertilizer, animal feed or bioenergy, producing pellets. IX X Bioenergy and industrial applications of grape pomace from “Vinho Verde” Resumo Portugal é o quinto maior produtor de vinho da UE-28 e o décimo primeiro no mundo, com uma produção estimada de 5,886 khL em 2014. Neste ano, na região Portuguesa do Minho a produção de “Vinho Verde” foi de 530 khL. O bagaço de uva (GP) é um resíduo agro- industrial composto de engaço, películas e grainhas, com peso de 20-25% do total das uvas utilizadas para a produção do vinho. No Minho são geradas por ano quase 18x103 ton de GP, resíduo que é utilizado para a alimentação animal, fertilizante ou depositado em campo aberto para biodegradação, causando problemas ambientais. A deposição não controlada do bagaço provoca fenómenos de fitotoxicidade e contribui para as emissões de GEE. O objetivo deste estudo foi avaliar o potencial de aplicação do bagaço de uva como bioenergia e matéria prima na indústria transformadora para obter produtos com valor acrescentado. Este estudo foi realizado no GP das variedades Loureiro e Vinhão, provenientes da Adega Cooperativa de Ponte da Barca. A composição química foi determinada através da análise do conteúdo de humidade, cinza, N-Kjeldhal, gordura, hidratos de carbono (HC), fibra, minerais, conteúdo fenólico total (TPC), atividade antioxidante, e identificação/quantificação de nove polifenóis, aplicando métodos analíticos de referência. O poder calorífico (HHV) foi determinado pelo método da Parr Instruments. A humidade no bagaço de uva varia de 42.2% a 72.8%. Na matéria seca foram obtidos os seguintes resultados, 3.3% a 7.9% em cinza, de 1.0% a 2.1% em N-Kjeldahl, de 2.0% a 16.4% em gordura, de 15.4% a 29.2% em HC, de 11.9% a 31.0% em fibra, 23.9 a 120 mg GAE/g em TPC e 12.2 a 83 mg AAE/g em DPPH. Comparando as duas variedades de GP, o Vinhão apresenta um teor mais elevado que o Loureiro em oito polifenóis, sendo exceção o resveratrol com 0.244 mg/g MS no Loureiro, valor próximo do mais elevado encontrado na literatura. O HHV do GP antes e após extração dos bioativos varia entre 17 e 21 MJ/kg, valor comparável com o mais elevado de biomassa florestal. Tendo em conta os resultados obtidos, conclui-se que o GP é um sub-produto muito valioso, podendo ser obtidos outros produtos num processo muito rentável. Na transformação do GP, primeiro devem ser isolados os bioactivos, posteriormente óleo de semente de uva e farinha sem glúten de uva para a nutrição humana e cosmetologia. Finalmente, o engaço pode ser usados como fertilizante, alimento para animais ou bioenergia (pelletes). XI XII Bioenergy and industrial applications of grape pomace from “Vinho Verde” Σύνοψη Η Πορτογαλία είναι η πέμπτη μεγαλύτερη χώρα παραγωγής κρασιού στην ΕΕ-28 και ενδέκατη στον κόσμο, με παραγωγή που εκτιμάται σε 5,886 khL το 2014. Την ίδια χρονιά στο νομό Minho η παραγωγή κρασιού «Vinho Verde» ήταν πάνω από 530 khL. Τα στέμφυλα, είναι αγροβιομηχανικά υπολείμματα που αποτελούνται από μίσχους, φλοιούς και σπόρους και αντιπροσωπεύουν περίπου το 20-25% του βάρους του σταφυλιού έπειτα από τη συμπίεση του κατά την οινοποίηση. Στον νομό Minho παράγονται ετησίως σχεδόν 18x103 τόνοι στέμφυλων, τα οποία χρησιμοποιούνται κυρίως για ζωοτροφές, λιπάσματα ή εναποτίθενται σε ανοιχτούς χώρους για βιοαποικοδόμηση, η οποία μπορεί να προκαλέσει σημαντικά περιβαλλοντικά προβλήματα. Η ανεξέλεγκτη απόρριψη αυτών των υποπροϊόντων προκαλεί φαινόμενα φυτοτοξικότητας και συμβάλλει στις εκπομπές αερίων του θερμοκηπίου. Ο στόχος της παρούσας μελέτης ήταν να αξιολογήσει τις δυνητικές εφαρμογές των στέμφυλων, σε βιοενέργεια και ως πρώτη ύλη για βιομηχανικές διεργασίες. Τα στέμφυλα που χρησιμοποιήθηκαν για τις αναλύσεις ήταν μια λευκή και μια ερυθρή ποικιλία ονόματι Loureiro και Vinhão, αντίστοιχα, που προήρθαν από τον οινοποιητικό συνεταιρισμό της Ponte da Barca.