high-volume chemicals from biomass · high-volume chemicals from biomass andré heeres, august...
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![Page 1: High-volume chemicals from biomass · High-volume chemicals from biomass André Heeres, August 2018. Content • Introduction (drivers for bio-based chemicals) • Strategies for](https://reader033.vdocuments.net/reader033/viewer/2022052720/5f084f217e708231d4215f1d/html5/thumbnails/1.jpg)
High-volume chemicals from biomass André Heeres, August 2018
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Content
• Introduction (drivers for bio-based chemicals)
• Strategies for conversion
• An example: bio-aromatics
• Thermochemical conversions
• Downstream to plastics
• Conclusions
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20th Century: The great acceleration
• Growth of population by a factor 3.7
• Annual extraction of construction materials grew by a factor of 34, ores and
minerals by a factor of 27, fossil fuels by a factor of 12, biomass by a factor of 3.6
• Total material extraction grew by a factor of 8
• GHG emissions grew by a factor of 13
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21th Century: Environment
• There is increasing evidence of the climate change threat
• 60% of ecosystems already degraded or used unsustainably
• 33% of soils is moderately to highly degraded due to erosion, nutrient depletion,
acidification, salinization, compaction and chemical pollution
• 467 000 premature deaths yearly in EU due to air pollution(7 millions globally)
• A million of plastic bottles are bought every minute. In 2015 9% of plastic was
recycled, 12% incinerated, 79% accumulated in landfills or the environment
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21th Century: Population
• Population growth (2050 – 9.7 billion)
• Per capita consumption growth (up to 3 billion consumers moving from low to
middle class consumption till 2030)
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21th Century: Urbanization
• Globally, an area of the size of the UK has been converted to buildings since
1990 (OECD GG Indicators 2017)
• More than 50% of urban fabric expected to exist by 2050 still needs to be
constructed
• In the three years period (2011-2013), China has used more cement than the
USA during the entire 20th century
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21th Century: Reaching the limits?
• In a world where external reserves resources are limited and our ecosystem is
under high pressure we need to navigate away from a potential crisis!
• Sustainable Consumption and Production, utilization of natural resources: an
attractive alternative?
• High-value chemicals and materials from biomass
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Top Value Added Chemicals from Biomass
NREL report 2004: Volume I—Results of Screening for Potential Candidates from
Sugars and Synthesis Gas
• Drop in/”novel” chemicals
• Synthetic routes- Biologically derived
- Chemically derived
• Criteria- Chemical functionality
- Market perspectives
- Uniqueness
- From cheap biomass
- Technical feasibility
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Drop in chemicals/Novel chemicals
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An example: “Green epichlorohydrin”
• Epichlorohydrin’: 2Mt/year (resins, polymers, crosslinker, etc.)
• Petrochemical route
• Surplus of glycerol (from biodiesel production)
• Synthesis from glycerol
• Large scale production (Solvay etc.)
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Drop in chemicals from bioethanol
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What about aromatics?
Drivers:
• Strong growth in global
plastics production
• Incentives to green up the
BTX business (BTX =
benzene, toluene, xylenes)
• Drop-in chemicals
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What about aromatics?
• Huge markets!
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Competition
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Catalytic pyrolysis
• Efficient one-step process
• Sustainable, low carbon footprint
• Non food and cheap biomass
• Rather cheap zeolite (H-ZSM-5) catalysts
• Moderate yields of BTX (5-25%, depending on biomass/conditions)
…….. but the “life time” of the catalyst??
• Restricted to dry biomass containing low amounts of inorganics.
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Ex situ catalytic pyrolysis
Pyrolysis
Advantages
• Extended life time of the catalyst
• Ability to use highly contaminated/wet biomass streams
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Mechanism
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Infrastructure used
Tandem microreactor (TMR)
• Ex situ aromatization
• Fast screening of catalysts and biomass
• Optimization
• BTX-yields
• Stability of the catalyst
Gram scale unit
• Mass balance
• Elemental balance
• Analysis products formed
• Yields BTX
• Yields bio-oil
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Results gram scale unitEx situ aromatization, T = 565 ⁰C, H-ZSM-5 (23); 0.3-0.5 mm, cat : biomass = 3:1
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Complex aqueous mixtures as a source
• Black liquor
- Widely available from pulp and paper industry (Kraft pulping)
• Complex and variable composition
- water (30%)
- organics (70%): lignin, tall oil, turpentine, depolymerized/oxidized
(hemi)cellulose fragments, and inorganic salts
• Up to 15-20% higher aromatics formed
Ex situ pyrolysis, T1 = 500 C
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GC analysis
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Ex situ catalytic pyrolysis
Pyrolysis
• Question: Discuss methods to improve the yield of BTX!
- Groups, 5-10 minutes
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Integrated Cascading Catalytic Pyrolysis (ICCP)
Hypothesis: A (cracking) catalyst could influences both the composition and
amount of the gaseous phase.Schenk, N.J., Biesbroek, A., Heeres, A., Heeres, H.J., Process for the preparation of aromatic compounds, WO2015047085.
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Integrated Cascading Catalytic Pyrolysis (ICCP)
TMR; pinewood : pyrolysis catalyst : (H-ZSM-5 (23) = 1 : 1 : 80, T1 = 550 ⁰C, T2 = 575 ⁰C)
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Recycle higher (reduced) aromatics
Co-feeding with PAH: slightly higher yields
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Recycle higher (reduced) aromatics
A. Heeres, N.J. Schenk, I Kruize-Muizebelt, WO2017/222380
Gram-scale unit, ex situ, T = 550º C, cat: biomass 3 : 1 (PCA G2 from crude glycerol)
• Co-feeding with polycyclic alkanes affords additional BTX!
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Stability of the catalyst
• H-ZSM-5 (23) ex-situ pyrolysis with intermediate oxidative catalyst regeneration (black liquor).
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Downstream: Towards green plastics
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BioPET100
• Drop-in chemicals; purification, separation and modification in existing (petrochemical) infrastructure
• Initial focus on p-terephthalic acid (PTA) and iso-phthalic acid (IPA)
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Pilot plant in progress
Acknowledgements
Prof. Erik. Heeres (RUG)
Dr. Niels Schenk (BioBTX)
Inouk Muizebelt (BioBTX)
Ricardo Blees (BioBTX)
Erwin Wilbers (RUG)
Cor Kamminga (BioBTX)
……..
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Conclusions
• Green resources are an attractive alternative for the synthesis of high
volume chemicals
• Ex situ catalytic pyrolysis has potential for large scale synthesis of
aromatics from biomass, including wet and highly contaminated
biomass streams.
• Outlets of the process are char (energy), gases/olefins (energy,
intermediates), BTX (intermediates chemical industry) and higher
aromatics (biofuel).
• Downstream processing afforded fully sustainable BioPET100.