Hydrothermal Liquefaction HTL - Innovhub

24-25 September 2015 Lodi HTL and pyrolysis for biocrude oil production from lignocellulosic biomass for biofuel applications or as chemical intermediates

Paolo Taddei Pardelli Spike Renewables Srl RE-CORD Consortium Florence, Italy Lodi September 24th, 2015

Outline • Introduction • Context, Aim and Objective • Company presentations Spike Renewables Srl and RE-CORD

• Ongoing Projects • Pyrolysis for bio-oil production

• Pilot plant • Pilot plant mass/energy balance • Building up new Flash Pyrolysis plant

• HTL for bio-oil production

• Pilot plant • Pilot plant Mass/Energy balance

• Feedstock and output • Conclusions

Lodi September 24th, 2015

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Context: Lignocellulosic Biomass Thermochemical Conversion Technologies Biomass Thermochemical Conversion Technologies such as Pyrolysis and HydroThermal Liquefaction (HTL) can directly convert lignocellulosic 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 renewables resources). Main parameters Pyrolysis

Parameter

HTL

400 -600

Temperature °C

280 – 370

Gas without O2 (anaerobic)

Media

Water

0-3

Pressure MPa

10 -25

1-2s (fast) 10-30s (interm.)

Residence time

up to 1h


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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. BIOGO is a 4-year collaborative project supported through the European Commission’s Nanosciences, nanotechnologies, Materials and new Production Technologies (NMP) theme. The project addresses topic 1.1-1 within this theme: Exploration, optimisation and control of nano-catalytic

processes for energy applications. BIOGO brings together fifteen Project Partners from seven countries. www.biogo.eu Lodi September 24th, 2015

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Ongoing Research Projects • LIDIA (SPRING National Technological Cluster of Green Chemistry): 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.

The aim of the project is to give concrete responses to find a valid and convenient alternative to petroleum for the production of chemical

products from renewable organic raw material (not in competition with the food chain).


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Spike Renewables SrL Spike Renewables SrL is an Engineering company composed by scientists from the University of Florence, Department of Energy CREAR (Research Center for Renewable Energy) and engineers with previous experience in General Electric Co. (Gas Turbine Division for Power Generation Applications). Focus on renewable energies: - Engineering of Electrical and Technological Systems in commercial, residential, industrial and healthy buildings – HVAC – Building Technology - CHP and Hydro Power EP - Concentrated solar power CSP-CPV - Biomass and bioenergy/biofuels processes and plants EP - Microalgae for biofuel pilot plant EP - Biomass thermochemical conversion - HTL – Flash Pyrolysis Patented Processes Lodi September 24th, 2015

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RE-CORD • RE-CORD was established as a public/private not for profit Research Centre (according to EU and National Legislation). • Members: University of Florence (CREAR and the Montepaldi farm), Spike Renewables Srl and Pianvallico SpA • RE-CORD Consortium combines skills and resources (personnel, laboratories and equipments) of its members, creating a critical mass able to develop research and activities of primary-level science and technology.


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Pilot units • • • • • • • • • • • • • • • •

Milling & Briquetting unit (100 kg/h) Torrefaction/Carbonisation unit (50 kg/h) Methanation reactor Hydrothermal Liquefaction HTL (15 l/h) reactor (with Spike) Microreactor system for hydrothermal carbonization & liquefaction 1.5 kg/h Intermediate Catalytic Pyrolysis Open-top twin-fire gasifier (100 kg/h, 70-100 kWe) Downdraft Imbert-type gasifier (10 kWe) Capstone Microturbine converted to biofuels (30 kWe) Garret Microturbine converted to biofuels (40 HP, 20 kWe) External Combustion Microgasturbine (50-100 kWe) Pure Veg.Oil MicroCHP (5 kWe/10 kWth) Pure Veg.Oil generators (7 e 50 kWe) Anaerobic digestors (2l-dynamic, BMP-static) Algae pilot plants (with DISPAA/F&M) Solar simulator for algae (SOSIA)


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RE-CORD pyrolysis pilot plant description Feeding system

Condenser

Biomass and N2

Heating electric power Mixer Bio oil and non cond. gases


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RE-CORD pyrolysis plant energy and mass balance

Lab plant is not a reference for energy balance; use of char and heat recovery may increase overall efficiency Energy required for the pyrolysis[1]: 1.6±0.3 MJ (kg-dry-biomass)-1 for pine [1] Daugaard D. E., and Brown R. C., 2003, “Enthalpy for Pyrolysis for Several Types of Biomass,” Energy & Fuels, 17(4), pp. 934–939.


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Spike HTL pilot plant description Patent Pilot Plant for biomass Hydro Thermal Liquefaction (HTL) PROPERTY: Spike Renewables Srl / RE-CORD n. FI2015A000127 date 29.04.2015 Filters

Reactor

Biomass and water Bio oil tank, non cond. gases and waste water

HP electric pump Pre-heating


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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]

[1] Toor, Rosendahl, Rudolf – 2011 – Hydrothermal liquefaction of biomass A review of subcritical water technologies


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Flash Pyrolysis reactor Patent Pilot Plant for biocrude oil production from lignocellulosic biomass by Flash Pyrolysis PROPERTY: Spike Renewables Srl n. FI102015000042343 date 05.08.2015 New Flash Pyrolysis Pilot Plant

• Innovative • Continuous • High efficiency arc lamp • Bio-oil main product • 10 kg/h biomass • 6/7 kg/h bio-oil


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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


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Feedstock influence on bio-oil

Pyrolysis

Parameter Biocrude yield (%) Energy recovery (%) N (%) O (%)

Lignocellulosics 55 51 0.4 43

Macroalgae 47 45 1.75 46

Microalgae 43 63 5 - 13 7 - 36

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, 2010.

HTL

Parameter Lignocellulosics 35 Biocrude yield (% daf) Energy recovery (%) 64 N (%) 0.3 O (%) 12

Macroalgae 27 52 6-8 6-8

Microalgae 38-64 60-78 4-8 5-18

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).


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Bio-oil comparison

Hydro Thermal Liquefaction Characteristics Moisture [wt%] 5 HHV [MJ/kg] 35.7 Viscosity [cPs] 15000 @ 61 °C Elemental analysis (db wt%) C 77 H 8 O 12

Pyrolysis 25 22.6 59 @ 41 °C 58 6 36

D.C. Elliott, G.F. Schiefelbein, Liquid hydrocarbon fuels from biomass, Am. Chem. Soc. Div. Fuel Chem. Annu. Meet. Prepr. 34 (1989) 1160–1166.


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Bio-oil derivatives: chemical intermediates Biomass constituent

Pyrolysis products (major valueadded chemicals underlined)

Market application examples of the underlined chemicals bulk-chemical, vinegar (food), cleansing agent, vinyl acetic acid, furfural, furan, furanone, thanol, other C1- acetate, acetic anhydride, esters, solvent, road Hemicellulose C4 oxygenates (e.g. formaldehyde, deicer (as calcium acetate), intermediate hydroxyacetaldehyde, acetone, acetol, lactones, etc), commodity chemical, solvent, resins, adhesives, (150-300°C) C5 and C6-anhydrosugars, humic substances food flavouring agent, precursor for specialty chemicals levoglucosan, hydroxyacetaldehyde, 1,6 anhydro-b-DCellulose glucose, polymers, antibiotics glucofuranose, furfural, hydroxymethylfurfural, furan, food browning agent in ‘liquid other C1-C4 oxygenates (e.g. methanol, formaldehyde, (200-400°C) smoke’ formic acid, acetone, acetol, lactones, etc) 2-methoxyphenols (e.g. guaiacol), 2,6fine chemicals, pharmaceuticals, food flavouring dimethoxyphenols (e.g. syringol), catechols, phenol, agents in ‘liquid smoke’, fragrance industry, bulkLignin alkyl-phenols methanol, other oxygenated aromatics chemical, wood-adhesives, resins, plastics, fuel (e.g. coumaran), furfural, acetic acid, other C1-C4 additives bulk-chemical, solvent, fuel, antifreeze, (150-600°C) oxygenates (e.g. formaldehyde, formic acid, acetone, ethanol denaturant, 2nd energy carrier for H2, bioacetol, lactones, etc) pyrolytic lignin diesel Whole fine chemicals, pharmaceuticals, turpentine, fuel, biomass extractives (e.g. terpenes), charcoal, pyrolysis-oil, soil improver, active carbon, metallurgy, BBQ, liquid gases (e.g. CO, CO2, CH4) fuel, feedstock for chemicals such as organic acids (100 -600°C) and phenolic compounds fuel


P. de Wild, H. Reith, E. Heeres, Biomass pyrolysis for chemicals, 2011. doi:10.4155/bfs.10.88.

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Conclusions • Spike Renewables Srl is an Engineering Company (SME) member of RE-CORD Consortium (University of Florence), with specific activities on innovative pilot plant design • Spike/RECORD have availability of Pyrolysis and HTL pilot Plants for biocrude oil production from biomass feedstocks • Partner profile: • SME for engineering of innovative pilot plant design; • Availablity of pilot plants for biofuel/bioproduct research activities and production


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Thanks for your attention!

Paolo Taddei Pardelli

Contacts www.spikerenewables.com [email protected]

[email protected]


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