2a GIORNATA NAZIONALE SUL BIOMETANO Biogas e biometano in Italia e in Europa: i progetti europei SEBE e GreenGasGrids

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1 2a GIORNATA NAZIONALE SUL BIOMETANO Biogas e biometano in Italia e in Europa: i progetti europei SEBE e GreenGasGrids Il progetto SEBE e le azioni pilota dell Environment Park: i pretrattamenti delle biomasse finalizzati all ottimizzazione della produzione di biogas Paola ZITELLA Environment Park Convegno Nazionale Progetto SEBE 10 maggio 2013

2 The science and technology park Environment park was founded on 1996, by an initiative of Piedmont Region, Province of Torino and City of Torino, and it s built on a former industrial area. Envipark is a private shared company with public shareholders Park mission is to provide SMEs support to develop innovative solutions in the fields of environmental and energy technologies

3 The Eco Site Environment Park site counts on 9 buildings, for an overall footprint of m 2, of which m2 built. The site has been conceived and built with the goal to reduce as possible environmental impacts and CO2 emissions. Green roofs Rain water recovery systems Wood chips for heating and cooling Thermal solar and heat recovery systems PV generator Eco-efficient building technologies Hydropower plant 06/02/2013

4 The service centre Entirely designed with green building criteria. Consumption Primary energy consumption 99,4 kwh/sqm instead of 146kWh/sqm consumed by a traditional building. Energy produced from RES 329,3 kwh/sqm instead of an average production of 27,8 kwh/sqm in traditional buildings Annual consumption of drinkable water 0,1 m3/sqm instead of 5 m3/sqm consumed by a traditional building.

5 Mission and Model The Park has the primary purpose to promote the development of applied environmental and energy research The Company operates along two main activity areas: 1)real estate management of Environment Park site 2)Technology transfer to enterprises in environmental and energy fields Activities are developed in an integrated way, where Real estate and Technology transfer actions mutually support each other in the achievement of statutory and economical targets. RE RE R&D R&D curia TECH./KNOW. TRANSFER BASIC APPLIED RESEARCH RESEARCH DEVELOPMENT

6 Domains of activities Presently four main technology areas, each one splitted into several technology platforms Technology platforms are structured with pilot plants, test facilities, technology projects Operational model: collaborative research with enterprises and Research bodies (main focus on SMEs) Internal personnel plus cooperation with academies

7 BioENERGY LAB is the laboratory of Environment Park dedicated to innovative technologies for energy production from biomass.

8 Biomass to Energy Lab BioENERGY LAB operates in the field of the development and optimization of technologies in the field of energy exploitation of organic materials Technology platforms are: Biomass pre-treatment Wood-cellulosic based materials Bio-hydrogen and biogas production from biomass Zootechnical waste treatment by algae processes Biogas to bio-methane upgrading processes

9 Bioenergy lab platforms Biomass pre-treatment Pilot plant testing three different technologies: Steam Explosion Chemical Hydrolysis Enzymatic Hydrolysis Bio-hydrogen and biogas production Pilot plant for controlled anaerobic fermentation Biogas to bio-methane Exploitation of biogas through injection in the NG grid and use as automotive fuel Algae processes Photo-bio-processes for agricultural waste treatment 06/02/201

10 SEBE PROJECT PILOT ACTION _ Technology Pre-Treatment Optimization for High-Biogas production Second generation biomass LIGNIN is the most complex natural polymer. IT CROSSLINKS different plant POLYSACCHARIDES, conferring mechanical strength to the cell wall Agricoltural residues (wheat straw) Agroindustrial residues (peel, cores, ) CELLULOSE is a polysaccharide a A POLYMER of GLUCOSE (C6H10O5)n It s present as a major structural component of cell walls and provides: mechanical strength chemical stability to plants HEMICELLULOSE is any of several heteropolymers with random amorphous structure with little strenght Hemicelluloses are embedded in the cell walls of plants in chains bind with pectin to cellulose Release fermentable sugars (eg, glucose, xylose, fructose,...) usable by anaerobic bacteria for biogas production Hydrolysis pretreatments

11 Organic wastes Fruits and vegetables peels (coming from Envipark canteen) Unsold and non edible stocks of fruits and vegetables (coming from supermarket) Residues from processes of vegetables cutting and washing (agro-industry) Wheat straw coming from farm (Coop. Speranza, Piedmont Region) Lignin (g/100g dry matter) Fruits and vegetables Agroindustrial Preliminary characterization residues Wheat Straw Cellulose Hemicellulo (g/100g dry se (g/100g matter) dry matter) ,64 38,26 27,9

12 PRETREATMENTS PROCESSES Pre-treatments combuination: steam explosion + enzymatic hydrolysis Lignocellulosic biomass 2 steps for production of fermentable sugars 1. Pretreatment process (chemical or physico-chemical) -acid or basic hydrolisys -steam explosion process Umid weath straw Steam explosion C for 3-5 Enzymatic Cellulose more accessible for further hydrolysis at 37 C ph for 24 h Hydrolysis of hemicellulose Pre-treated conversion straw Separation/condensation of lignin + fraction Pre-treatments combination: chemical hydrolysis enzimatic hydrolisys 2. Enzymatic hydrolisys: use of enzymes mix (cellulase, hemicellulase, pectinase,lignin peroxidase etc.) Umid weath straw Chemical hydrolysis Enzymatic Hydrolisys of cellulose, hemicellulose HCl o H2SO4 at hydrolysis at 37 C 120 C for 2-3 h ph for 24 h etc Pre-treated straw DRAWBACK formation of toxic compounds: furfural, HMF, vanilline, syringaldeide, levulinic acid etc. INHIBITORS FOR FURTHER STEPs (LIKE FERMENTATION

13 Steam explosion- description Tank V-101 Reactor R-101 V=22 lt (2 kg of biomass/cycle) Pmax= 26 bar Tmax=227 C Pre-heating jacket V=10 lt Temperature and pressure control system V=300 lt for the expansion Pmax= 1 bar Cooling jacket Hermetic butterfly valve for the recovery of the exploded biomass

14 Chemical Hydrolisis Chemical hydrolisis- description V=115 lt Pmax=4.5 bar,a Tmax=120 C Heating (and cooling) jacket (low pressure steam) Pmax, jacket= 3 bar,a Tmax, jacket= 134 C Acid and basic dosage tanks for the immission of reactants through dosage pumps (62 lt/h manually adjustable)- ph regulation Paddle Stirrer (max 650 r.p.m.)- STR Temperature control through the immision of steam/cooling water in the heating jacket (pneumatic regulation valve) Split range pressure control through the immission of inert gas and vent

15 Enzymatic hydrolisis V=115 lt Pmax=1.7 bar,a Tmax=70 C Heating (and cooling) jacket (etylene glycol) Reactant dosage tanks for the immission of reactants through dosage pumps (62 lt/h manually adjustable) Paddle Stirrer (max 650 r.p.m.)- STR Fine temperature control through 2 plate heat exchangers (water-etylene glycole for cooling and steam-etlyene glycole for heating) Split range pressure control through the immission of inert gas and vent Reactor of enzymatic hydrolisis R-103 Cooling E-102 Heating E-103

16 Combined pretreatment on wheat straw CE SE Steam explosion + enzymatic hydrolysis Steam explosion at 190 C for 5 (Datar et al., 2007) New enzymatic mix with Cellulase from Trichoderma Sp. Hemicellulase from Aspergillus niger Xylanase from trichoderma longibrachia T=37 C ph=4.5 Kinetic characterization of the process for the identification of the treatment optimal duration Chemical pretreatment+ enzymatic hydrolysis H2SO4 at different concentration (0.5 N-1N) Temperature ~120 C Duration 2.5 h New enzymatic mix with Cellulase from Trichoderma Sp. Hemicellulase from Aspergillus niger Xylanase from trichoderma longibrachia T=37 C ph=4.5 Kinetic characterization of the process for the identification of the treatment optimal duration

17 Yields of mobilization of fermentable sugars Wheat Straw- Chemical+Enzymatic CONDITIONS TYPOLOGY OF ENZYME ANTIBIOT TEMPERAT BUFFER PH PRETREATMENT CONCENTRATION IC URE Test Yield of 0.1Yield of Yield of Yield of Total % kg cellulase/kg of Acid Pretreatment glucose glucose at t=0 xylose xylose (glucose+xyl theoret with H2SO4 2.5% (0.5 dry biomass (% (% ose) hical TEST 0.1 kg hemicellulase/kg 37 C 4.5 N) wt/v for 2.5 h at theoret theoret of dry biomass at t=0 CE1 120 C hical) hical) 0.1 kg xylanase/kg of dry biomass at t=0 CE gr/100gr 66.5 % lt/kg33.7 % 39.1 gr/100gr 52.6 % 5.0 (t=0 0.1 kg cellulase/kg of of dry Acid Pretreatment 37biomass C (t=0 h) h) of dry biomass gr/100gr of of dry dry biomass at t=0 biomass 0.1 g/kg 40 C (t=89 h) 4.5 (t=89 with H2SO4 2.5% (0.5 dry biomass TEST 0.1 kg hemicellulase/kg dry 30 C (t=187 h) N) wt/v for 2.5 h at of dry biomass at t= M of CE2 CE gr/100gr 85% 16.5 sodium-52 biomass % 52.6 gr/100gr 70.9 h) 4.5% 120 C of of dry biomass0.1 kg xylanase/kg gr/100gr of of dry biomass citrate (t=187 h) dry biomass at dry t=187 biomass buffer TEST CE3 CE gr/100 gr0.1 kg 80.9 % 14.8ofgr/100 cellulase/kg Acid Pretreatment of dry biomass dry biomass at t=0 gr of dry with H2SO4 5% (1 N) biomass 0.1 kg hemicellulase/kg wt/v for 2.5 h at of dry biomass at t=0 120 C 0.1 kg xylanase/kg of dry biomass at t= % 49.2 gr/100 gr of dry biomass 37 C 66.3 % 4.5

18 Conc. Glu (g/lt) Conc Glu (g/lt) Runtime (h) Runtime (h)

19 SE Tests on wheat straw- Steam Explosion process CONDITIONS P=13 bar T=190 C t=5 min Severity=2.233 min Pretreatment: cutting and water impregnation

20 SE Tests on wheat straw- Steam Explosion process Degradation of lignin, cellulose and hemicellulose

21 SE Steam Explosion Conditions Enzymatic Hydrolysis Conditions SE1 190 C, 5 minutes 0.01 kg of cellulase/kg of biomass 0.01 kg of hemicellulase/kg of biomass 0.01 kg of xylanase/ kg of biomass ph=4.5 ph=4.5 T=37 C SE2 190 C, 5 minutes 0.1 kg of cellulase/kg of biomass 0.1 kg of hemicellulase/kg of biomass ph=5 0.1 kg of xylanase/ kg of biomass ph=4.5 T=37 C SE3 190 C, 5 minutes 0.1 kg of cellulase/kg of biomass 0.1 kg of hemicellulase/kg of biomass 0.1 kg of xylanase/ kg of biomass ph=5 T=37 C SE4 190 C, 5 minutes 0.01 kg of cellulase/kg of biomass 0.01 kg of hemicellulase/kg of biomass 0.01 kg of xylanase/ kg of biomass ph=5 T=37 C

22 Conclusion on chemical and enzymatic treatments on straw Higher concentration (1N vs 0.5N) of acids improve the mobilization of glucose in the following enzymatic treatment but increases the duration of treatment Feeding the mixture of enzymes separately increases the mobilization of glucose and xylose but it increases the duration of treatment Conclusion on Steam explosion+enzymatic Hydrolysis on straw Tests on wheat straw Total Degradation of lignin, cellulose and hemicellulose in the solid part Very low concentration of xylose in the final hydrolysate Higher concentration of glucose are achieved with the highest concentrations of the different enzymes (0.1 kg/kg of dry biomass) Higher concentrations of glucose are achieved working at ph=4.5 in the enzymatic hydrolysis

23 Organic Residues pre-treatments First panel of test Chemical pretreatment + Enzymatic Hydrolysis For this kind of biomass, two different kinds of chemical treatment have been tested: Acid pretreatment (HCl 1N and 5N) at 50 C for 24 hours Basic pretreatment (NaOH 1N and 5N) at 50 C for 24 hours Enzymatic treatment has been performed by using a combination of commercial cellulase+cellobiase (1 mg/g of dry biomass) working at 37 C and ph=5.5 for 24 hours

24 Second panel of test The organic wastes has been collected from Environment Park canteen and it contained the following typology of fruits and vegetables; A mechanical pretreatment has been performed by chopping the mixture in order to reduce the size of solid particles and increase the surface area for subsequent enzyme activity. Typology of waste Potato peels Carrot peels Orange peels Green salads waste % wt 16,1% 28,0% 28,0% 28,0%

25 CONDITIONS FOR CHEMICAL PRETREATMENT HCl 1N at 50 C Sample A for 1h HCl 1N at 121 C Sample B for 1h NaOH 5N at Sample C 50 C for 1h NaOH 5N at Sample D 121 C for 1h H2SO4 0.5N at Sample E 50 C for 1h H2SO4 0.5 N at Sample F 121 C for 1h CONDITIONS FOR ENZYMATIC PRETREATMENT Sample A Sample B Sample C Sample D Sample E Sample F Sample G Only Enzyme without previous chemical treatment 50 gr of enzyme/kg of raw biomass ph=4.0 T=50 C

26 Conclusion on chemical and enzymatic treatments on organic wastes Chemical treatments Acid reagents seem to be more effective in sugars extractions respect to base in comparable process conditions Treatments with sulphuric acids are more effective than these with chloride acid Test with sulphuric acid 0,5 N are more efficient than those with acid 1 N Test at higher temperature (121 C) are more valuable than those at 50 C

27 Enzymatic treatments Higher values in Glucose extraction with the combination of acid treatment with sulphuric acid 0,5 N at 121 c in combination with pectinase enzymatic treatment (50 gr of enzyme/kg of raw biomass, ph=4.0-t=50 C) Pectinase enzymes seems more proficient in sugar extraction than the combination of cellulase and cellobiase for these kind of substrates At the same condition of enzymes type and concentration and process time and temperature the results obtainable form enzymatic treatments are strongly related to the preliminary chemical treatments After 24 h of treatment, the activity of the enzyme does not seem to express anymore: this could be due to some fermentative degradation phenomena occurring despite the antibiotic addition since that the dosage may be insufficient or its spectrum is not quite broad Pectinase enzymes treatment without chemical pre-treatment could reach the same results in terms of sugars extraction but with longer residence time (70h instead of 24h)

28 Conclusions Cereal straws are a very important source of raw material since the world production is about 1700 million tons/year. Considering that one kilogram of cereals generates approximately one kilogram of residues this agricultural activities creates a huge quantity of residues that are used nowadays, at best and in small quantities, as organic amendment and food for cattle, but mostly they are burned with pollution generation. Environment Park activity developed till now has allowed the extraction of simple sugars from straw rise up to 52,6 g/100g of dry biomass (about the 70,9% of the theoretical content). From 1 kg of glucose is it possible to produce about 750 L of biogas This could result in an improved potential in biogas generation from unexploited wastes that can rise up to million Nm3/y.

29 2a GIORNATA NAZIONALE SUL BIOMETANO Biogas e biometano in Italia e in Europa: i progetti europei SEBE e GreenGasGrids Thank you! Parco Scientifico Tecnologico per l Ambiente Via Livorno 60, TORINO (Italy) paola.zitella@envipark.com Convegno Nazionale Progetto SEBE 10 maggio 2013