September Paolo Taddei Pardelli Spike Renewables Srl RE-CORD Consortium Florence, Italy

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1 September 2017 Spike Renewables Srl -SME Partner Profile Engineering and Prototyping Activities Paolo Taddei Pardelli Spike Renewables Srl RE-CORD Consortium Florence, Italy

2 Spike Renewables SrL Spike Renewables S.r.l. is an Engineering Company focused on system engineering that deals with all aspect of a project from design to construction and integration. Focus on renewable energies: - Biomass and bioenergy/biofuels processes and plants Engineering - Organic by-products thermochemical conversion by HTL and Flash Pyrolysis Patented Processes - Engineering of Electrical and Technological Systems in industrial, commercial and residential buildings HVAC Building Technology - Spike is founder member of RE-CORD (Renewable Energy Consortium for Research and Demonstration), University of Florence no profit Spin-off

3 Ongoing Research Projects BIOGO-for-production (FP7) - : Catalytic Partial Oxidation of Bio Gas and Reforming of Pyrolysis Oil (BioOil) for an Autothermal Synthesis Gas Production and Conversion into Fuels. SMARTREC (H2020) - : Developing a standard and modularized solution for flexible and adaptive integration of Heat Recovery and Thermal Storage for high grade waste heat by Molten Salts as Heat Transfer Fluid. LIDIA (Cluster Spring) - : Development of second generation technologies for the conversion of organic derivates in green dicarboxylic acids as building blocks of renewable origin for the synthesis of chemicals and polymers.

4 Context: Biomass Feedstock Thermochemical Conversion Technologies Biomass Thermochemical Conversion Technologies such as Pyrolysis and HydroThermal Liquefaction (HTL) can directly convert biomass into a liquid biocrude oil. The process outcome biocrude oil is then a chemical intermediate for bio-chemical products or for bio-fuel applications (from renewable resources). Main parameters Pyrolysis Parameter HTL Temperature C Low oxygen gas Media Water 0-3 Pressure MPa s (fast) 10-30s (interm.) Residence time up to 1h

5 Spike HTL pilot plant description Patent Pilot Plant for biomass Hydro Thermal Liquefaction (HTL) PROPERTY: Spike Renewables Srl / RE-CORD n. FI2015A date HP HT Filters Cooling section Biomass and water Reactor Bio oil tank, non cond. gases and waste water HP electric pump Pre-heating

6 Spike HTL plant balance Lab plant is not a reference for energy balance; use of char and heat recovery may increase overall efficiency. Specific energy consumption based on design installed power brings to 97 MJ/kg (bio oil acetone soluble) [1] [1] Toor, Rosendahl, Rudolf 2011 Hydrothermal liquefaction of biomass A review of subcritical water technologies

7 DEVELTAR: TAR removal and Conversion New gas way DEVELTAR module DEVELTAR Module In line insertion Collecting tar from producer gas Air-blown tar re-gasification through microwave-assisted heating Improving producer gas spec. Dry system Torch Burned gas Biomass Air Reactor Producer gas High T cyclone Existing gas line Metallic diaphragm Original gas way

8 Flash Pyrolysis reactor Patent Pilot Plant for biocrude oil production from lignocellulosic biomass by Flash Pyrolysis PROPERTY: Spike Renewables Srl n. FI date New Flash Pyrolysis Pilot Plant Innovative reactor Continuous High efficiency arc lamp Bio-oil main product capacity 10 kg/h biomass production 6/7 kg/h bio-oil

9 MSTP Molten Salts Test Plant A Molten Salt Test lab Plant (MSTP) has been designed and will be assembled to test different molten salts under real operational conditions and therefore understand critical issues and technological problems before moving to full demonstration scale.

10 Conclusions Spike Renewables Srl is an Engineering Company (SME) founder member of RE- CORD Consortium (University of Florence), with specific activities on innovative pilot plant design; Partner profile: SME for engineering of innovative industrial and pilot plant design and prototyping; Availability of pilot plants for bio crude oil production for biofuel/bioproduct research activities and production (HTL Pyrolysis); Availability of Molten Salt Test Plan for Heat Recovery for Industrial applications, research activities and energy savings (MSTP).

11 Thanks for your attention! Paolo Taddei Pardelli Contacts

12 Feedstock Pyrolysis Parameter HTL Very low Water content irrelevant 1-20 mm Size < 1mm Drying Pre-processing Milling Yes (dried) Lignocellulosic Yes (milled) Yes (dried) Algae Yes (as harvest) No Sewage / Sludge Yes Waste gas treatment Issues Waste water treatment Typical biomass

13 Feedstock influence on bio-oil Pyrolysis Parameter Lignocellulosics Macroalgae Microalgae Biocrude yield (%) Energy recovery (%) N (%) O (%) K. Chaiwong, 2013; M. C. C. Maguyon, 2013; K. Wang, 2013; F. Delrue 2014; J. Hyung, 2014; Z. Du, 2011; Z. Hu, 2013; C. E. Greenhalf, 2013; A. Oasmaa, HTL Parameter Lignocellulosics Macroalgae Microalgae Biocrude yield (% daf) Energy recovery (%) N (%) O (%) D.C. Elliott, P. Biller, A.B. Ross, A.J. Schmidt, S.B. Jones, Hydrothermal liquefaction of biomass: Developments from batch to continuous process, Bioresour. Technol. (2014).

14 Bio-oil comparison Hydro Thermal Liquefaction Characteristics Pyrolysis Moisture [wt%] 5 25 HHV [MJ/kg] Viscosity [cps] 61 C 41 C Elemental analysis (db wt%) C H 8 6 O D.C. Elliott, G.F. Schiefelbein, Liquid hydrocarbon fuels from biomass, Am. Chem. Soc. Div. Fuel Chem. Annu. Meet. Prepr. 34 (1989)

15 Bio-oil derivatives: chemical intermediates Biomass constituent Hemicellulose ( C) Cellulose ( C) Lignin ( C) Whole biomass ( C) Pyrolysis products (major valueadded chemicals underlined) acetic acid, furfural, furan, furanone, thanol, other C1- C4 oxygenates (e.g. formaldehyde, hydroxyacetaldehyde, acetone, acetol, lactones, etc), C5 and C6-anhydrosugars, humic substances levoglucosan, hydroxyacetaldehyde, 1,6 anhydro-b-dglucofuranose, furfural, hydroxymethylfurfural, furan, other C1-C4 oxygenates (e.g. methanol, formaldehyde, formic acid, acetone, acetol, lactones, etc) 2-methoxyphenols (e.g. guaiacol), 2,6- dimethoxyphenols (e.g. syringol), catechols, phenol, alkyl-phenols methanol, other oxygenated aromatics (e.g. coumaran), furfural, acetic acid, other C1-C4 oxygenates (e.g. formaldehyde, formic acid, acetone, acetol, lactones, etc) pyrolytic lignin extractives (e.g. terpenes), charcoal, pyrolysis-oil, gases (e.g. CO, CO2, CH4) Market application examples of the underlined chemicals bulk-chemical, vinegar (food), cleansing agent, vinyl acetate, acetic anhydride, esters, solvent, road deicer (as calcium acetate), intermediate commodity chemical, solvent, resins, adhesives, food flavouring agent, precursor for specialty chemicals glucose, polymers, antibiotics food browning agent in liquid smoke fine chemicals, pharmaceuticals, food flavouring agents in liquid smoke, fragrance industry, bulkchemical, wood-adhesives, resins, plastics, fuel additives bulk-chemical, solvent, fuel, antifreeze, ethanol denaturant, 2nd energy carrier for H2, biodiesel fine chemicals, pharmaceuticals, turpentine, fuel, soil improver, active carbon, metallurgy, BBQ, liquid fuel, feedstock for chemicals such as organic acids and phenolic compounds fuel P. de Wild, H. Reith, E. Heeres, Biomass pyrolysis for chemicals, doi: /bfs