Hydrothermal liquefaction of microalgae to produce a bio-binder: feedstock type influence
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1 June 19 th 21 st, 2018 Hydrothermal liquefaction of microalgae to produce a bio-binder: feedstock type influence Ilef BORGHOL Clémence QUEFFELEC, Emmanuel CHAILLEUX, Bruno BUJOLI, Jack LEGRAND, Delphine DROUIN, Christophe LOMBARD Paper N : 95
2 Searching for petroleumbased bitumen alternatives, why? Bitumen : comes from petroleum refinery Petroleum: fossil fuel, nonrenewable, influenced by geopolitical and socio-economic concerns World bitumen annual production estimated : 122,5 MT / year in Pavement construction (90%) - Roofing membrane manufacture Anticipate new alternatives to petroleum bitumen Search for efficient routes to produce bitumen substitutes from renewable biomass sources 2
3 Alternatives Why not microalgae? Feedstock supply o Rapid growth o Biodiversity > o High photosynthetic yield o No competition with more noble uses AlgoSource Technologies (Assérac, Loire-Atlantique, France) Micralgae residues are provided by Algosource Technologies (Assoérac, Loire-Atlantique, France) growing in open raceway water soluble proteins were extracted for another valorization Phytochem. 1976, 18, 51 Ultrason. Sonochem. 2013, 20, 95 J. Soc. Bio. 2008, 202, 201 3
4 Microalgae residues studied Two residues studied: initial composition Scenedesmus sp. residues Spirulina sp. residues Scenedesmsus sp Spirulina sp. 28% 22% 27% 35% 20% 30% 17% 21% Lipids Proteins Carbohydrates Others 4
5 Hydrothermal liquefaction (HTL): Green transformation process Mimic the conditions under which petroleum naturally occurred (high pressure and temperature) Clean process : no organic solvent Wet biomass : no drying step Binder : - Hot melt - Viscoelastic - Sticky - Hydrophobic How to get a material similar to petroleum bitumen? 5
6 From microalgae residues to bio-binder: A challenge Two microalgae residues types tested: Scenedesmsus sp. and Spirulina sp. HTL parameters: Temperature: 260 C Load factor: 0.6 Aqueous fraction Gaz (CO 2 ) Hydrophobic fraction = Green binder ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
7 From microalgae residues to bio-binder: A challenge Microalgae residues Hydrophobic fraction (%) Aqueous fraction (%) Scenedesmus sp. 50 ±0,5 21 ±1,5 Spirulina sp. 48 ±1 32 ±0,5 GCxGC MS, H 1 NMR, FTIR Aromatic compounds, mainly based on phenol and indole derivatives Highly aliphatic compounds, including (a) long chain alkenes likely resulting from the decarboxylation of fatty acids (b) free fatty acids and their amide derivatives ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
8 δ( ) From microalgae residues to bio-binder: A challenge What influence have the feedstock type on bio-binders rheological properties Standard bitumen (35/50) : A viscoelastic behavior: elastic solid at low temperatures and a viscous Newtonian liquid at high temperatures Black curves Standard bitumen (35/50) E+01 1E+03 1E+05 1E+07 1E+09 G* (Pa) ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
9 δ( ) From microalgae residues to bio-binder: A challenge What influence have the feedstock type on bio-binders rheological properties Standard bitumen (35/50) : A viscoelastic behavior: elastic solid at low temperatures and a viscous Newtonian liquid at high temperatures Scenedesmus sp. bio-binder: A viscoelastic behavior similar as a standard petroleum bitumen (35/50) Black curves 100 Scenedesmus sp. bio-binder Standard bitumen (35/50) E+01 1E+03 1E+05 1E+07 1E+09 G* (Pa) ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
10 δ( ) From microalgae residues to bio-binder: A challenge What influence have the feedstock type on bio-binders rheological properties Standard bitumen (35/50) : A viscoelastic behavior: elastic solid at low temperatures and a viscous Newtonian liquid at high temperatures Scenedesmus sp. bio-binder: A viscoelastic behavior similar as a standard petroleum bitumen (35/50) Black curves 100 Spirulina bio-binder Scenedesmus sp. bio-binder Standard bitumen (35/50) E+01 1E+03 1E+05 1E+07 1E+09 G* (Pa) ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
11 δ( ) From microalgae residues to bio-binder: A challenge What influence have the feedstock type on bio-binders rheological properties Standard bitumen (35/50) : A viscoelastic behavior: elastic solid at low temperatures and a viscous Newtonian liquid at high temperatures Scenedesmus sp. bio-binder: A viscoelastic behavior similar as a standard petroleum bitumen (35/50) Spirulina sp. bio-binder: Rheological behavior similar to elastomer used as additives in petroleum bitumen Black curves Spirulina bio-binder Scenedesmus sp. bio-binder Standard bitumen (35/50) Elastomer rich binder E+01 1E+03 1E+05 1E+07 1E+09 G* (Pa) ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
12 G* (Pa) δ ( ) From microalgae residues to bio-binder: A challenge What influence have the feedstock type on bio-binders rheological properties 1E+09 1E+08 1E+07 1E+06 1E+05 1E+04 1E+03 1E T ( C) Scenedesmus sp. bio-binder Spirulina sp. biobinder Standard bitumen Elastomer rich binder Scenedesmus sp. bio-binder: the most rigid of all binders Spirulina sp. bio-binder: less sensitive to temperature than Scenedesmus sp. and standard bitumen especially in the high temperature domain Isochronous curves at 1 Hz T ( C) ACS Sustain. Chem. Eng. 2015, Green Chem, 2018,
13 G* (Pa) From microalgae residues to bio-binder: A challenge HTL temperature influence on Spirulina sp. bio-binder stiffness Isochronous curves at 1 Hz 1,E+09 1,E+08 1,E+07 1,E+06 T= 240 C T= 260 C T= 280 C T= 300 C Conventional bitumen 35/50 HTL temperature increase bio-binder stiffness decrease Possibility of change the bio-binder stiffness by adjusting the HTL temperature 1,E+05 1,E+04 Using bio-binders in substitution of different conventional bitumen grades 1,E+03 1,E T ( C) Green Chem, 2018,
14 Conclusions and outlooks: A promising bio-binder production process Results - Chemical characterization: hydrophobic fraction which consisted of an oily fatty acid-based fraction mixed with organic and inorganic solid residues - Rheological behavior is influenced by the feedstock type: * Scenedesmus sp. bio-binder petroleum-based bitumen Might be used as a direct alternative * Spirulina sp. bio-binder Binder loaded with a high percentage of elastomers Might be used as a bitumen modifier - Possibility of change the bio-binder stiffness by adjusting the HTL temperature Outlooks - Understand more deeply HTL (especially reactions mechanism) - Determine the influence of catalyst on the bio-binder rheological properties - Study on scaling influence: from laboratory batch to continuous HTL pilot 14
15 Acknowledgments Christophe LOMBARD Pr Jack LEGRAND Delphine DROUIN Bruno Bujoli Clémence QUEFFELEC Emmanuel CHAILLEUX 15
16 Thank you for your attention 16
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