A sustainable pathway to Work Programme 2016 - convert volatile - PowerPoint PPT Presentation

A sustainable pathway to Work Programme 2016 - convert volatile fatty acids 2017 Call CIRC-05-2016 coming from fermented food waste into bio-based solvents L. di Bitonto, C. Pastore 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Green Biobased-Chemicals Ethyl esters of VFAs Carburant i RCOOEt R= -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Linking the urban biowaste biorefjnery with existing waste/wastewater treatment facilities and with plastic industry Wastewater treatment – water line Wastewa Clean Primary Activated Secondary ter water to settling sludge settling discharge secondar Agro- y sludge primary Biogas industry sludge Anaerobic waste Acid digestion Fermentati Digestate on OFMSW (nutrients) PHA Park/ Sludge line Productio garden n management Pretreatmen PHA PHA PHA t Extracti processin processing Bioplastics Bio-based g on Biocomposit plastics Waste Concentratio Fibers es Biosolven n/ Plastic Fibers processi ts Estherifjcatio Compos ng processin industry n t g Water stream Sludge or solid stream Gas stream Internal water recycle not reported Integration with WW treatment 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT Solvent stream 26-29 June 2019, Heraklion, Crete Island, Greece

FROM URBAN BIO-WASTE • the organic fraction from separate collection of municipal solid waste ( 55 g TS/d from OFMSW ) • excess sludge from treatment of urban wastewater ( 39 g TS /d from WWS ), with possible further integration with wastewater treatment (water line) • garden and parks waste • possibly, some waste from food-processing facilities (to be selected, based on similar composition) TO BIO-BASED PRODUCTS • polyhydroxyalkanoate (PHA), a biodegradable natural biopolymer • related PHA-based bioplastics (e.g through blends) • fjbers (to be also used for PHA- based biocomposites). • bio-based solvents (to be also used in PHA extraction) 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Green Biobased-Solvents Acetic Acid Propionic Acid Butyric Acid Lactic Acid VFAs Ethyl-Esters 1 2 of VFAs Ethanol Food Waste To be used in Extraction of PH Alcohols (Task 2.4) Fermented FW CONCEPTUAL SCHEME 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

State of the art of production of Ethyl Esters State of the art of production of Ethyl Esters of VFAs of VFAs cat RCOOH + EtOH RCOOEt + H 2 O R = CH 3 ; CH 3 CH 2 ; CH 3 CH 2 CH 2 In the case of Acetic Acid Molar ratio RCOOH:EtOH of 1:1, T in the range (310-350 K), Nature of Catalysts NO co-solvents Final equilibrium yields does not exceed 1. Mineral Acids (homogeneous and heterogenised) 70%mol in Ethyl Acetate 2. Cationic Resins 3. Zeolites T echnical solutions adopted to improve EE 4. Metal Oxides yields: 5. Metal phosphates and or sulphate - Use of molar excess of reactants (EtOH) 6. Enzymes (free and supported) - Physical removal of Water (Special 7. Ionic Liquids reactors, Distillative column, reactive column, etc.) - Chemical Removal of water (chemical traps, zeolites, etc.) 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Production of Ethyl-Esters of VFAs: Production of Ethyl-Esters of VFAs: Drawbacks Drawbacks cat RCOOH + EtOH RCOOEt + H 2 O R = CH 3 ; CH 3 CH 2 ; CH 3 CH 2 CH 2 - Unfavourable Thermodynamics (low fjnal yields and Acids Conversion) The use of classic homogeneous mineral acids as catalysts (H 2 SO 4 , HCl, p-toluen sulphonic acid, etc.) has the following relevant drawbacks: - Highly Corrosive; - Not-easily recoverable from fjnal mixture - Production of a fjnal waste (salt) - High-Energy demanding procedure (azeotropic distillation) for the Recovery of Ethyl-Esters from the resulting mixture di Bitonto, L., Pastore, C. (2019) Renewable Energy, 143, pp. 1193-1200 Res Urbis approach: di Bitonto et al. (2016) Renewable Energy, 90, pp. 55-61 AlCl 3 ·6H 2 O was tested as a catalyst Pastore et al. (2015) Applied Catalysis A: General, 501, pp. 48-55 Pastore et al. (2014) Biores T echnol, 155, pp. 91-98 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Production of Ethyl-Esters of VFA: preliminary investigation on pure organic Production of Ethyl-Esters of VFA: preliminary investigation on pure organic acids (1) acids (1) RCOOH + EtOH RCOOEt + H 2 O R = CH 3 ; CH 3 CH 2 ; CH 3 CH 2 CH 2 70 70 70 60 60 60 Conversion / % 50 50 50 40 40 40 30 30 30 70 °C 70 °C 70 °C 60 °C 60 °C 60 °C 50 °C 20 20 20 50 °C 50 °C 40 °C 40 °C 40 °C No catalyst 70 °C 10 10 10 0 0 0 0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500 Butyric Acid Propionic Acid Acetic Acid Time / min 2-5 0,9-2 0,3 Efgect of T and R on kinetics and fjnal equilibrium composition 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Production of Ethyl-Esters of VFA: preliminary investigation on pure organic Production of Ethyl-Esters of VFA: preliminary investigation on pure organic acids (2) acids (2) RCOOH + EtOH RCOOEt + H 2 O R = CH 3 ; CH 3 CH 2 ; CH 3 CH 2 CH 2 Homogeneous second order model is applicable In the case of a molar ratio RCOOH:ROH=1:1* In which X eq , X t , [RCOOH] t0 and k 1 represent respectively the Acid conversion at the equilibrium , at the t time, starting molar concentration of the organic acid and the kinetic constant for the forward reaction. *Altıokka & Çıtak, Applied Catalysis A: General 239 (2003) 141–14 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Production of Ethyl Esters of VFA: preliminary investigation on pure organic Production of Ethyl Esters of VFA: preliminary investigation on pure organic acids (3) acids (3) Y Time / min Acid E a KJ mol Arrhenius Equation -1 Acetic 22.3 Propioni 22.8 c Butyric 35.8 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Intensifjcation of the process: optimization of operative conditions in order to improve the production and the simultaneous separation of products AlCl 3 . 6H 2 O HCl, . H 2 SO 4 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Production of Ethyl-Esters of VFA: preliminary investigation on pure organic Production of Ethyl-Esters of VFA: preliminary investigation on pure organic acids (5) acids (5) RCOOH + EtOH RCOOEt + H 2 O R = CH 3 ; CH 3 CH 2 ; CH 3 CH 2 CH 2 70 70 70 60 60 60 Conversion / % 50 50 50 40 40 40 30 30 30 70 °C 70 °C 70 °C 60 °C 60 °C 60 °C 50 °C 20 20 20 50 °C 50 °C 40 °C 40 °C 40 °C No catalyst 70 °C 10 10 10 0 0 0 0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500 Butyric Acid Propionic Acid Acetic Acid Time / min 2-5 0,9-2 0,3 Efgect of T and R on kinetics and fjnal equilibrium composition 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Intensifjcation of the process: Efgect of the amount of catalyst on the Intensifjcation of the process: Efgect of the amount of catalyst on the phase behaviour (1) phase behaviour (1) 1. Synthetic solution with EtOH, AcOH, AcOEt and H 2 O in their equilibrium composition is perfectly homogeneous 11 2. Addition to this solution of conventional mineral Acids did not produce any change 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Intensifjcation of the process: Efgect of the amount of catalyst on the Intensifjcation of the process: Efgect of the amount of catalyst on the phase behaviour (2) phase behaviour (2) 0 1% 2% 3% 4% 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece

Intensifjcation of the process: Efgect of the amount of catalyst on Intensifjcation of the process: Efgect of the amount of catalyst on the phase behaviour (3) the phase behaviour (3) Upper phase 100 Lower phase 90 1; 92.8 80 2; 87.4 3; 83.2 4; 79.4 70 5; 76.0 With the increase of the 60 %wt catalyst, the reaction 50 became fast and the 40 5; 24.0 bottom aqueous phase 30 4; 20.6 3; 16.8 20 2; 12.6 increased. 1; 7.2 10 0 0 1 2 3 4 5 . 6H 2 O (%mol) AlCl 3 7 TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT 26-29 June 2019, Heraklion, Crete Island, Greece