High-volume chemicals from biomass
André Heeres, August 2018Content
• Introduction (drivers for bio-based chemicals)
• Strategies for conversion
• An example: bio-aromatics
• Thermochemical conversions
• Downstream to plastics
20
th
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
21
th
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
21
th
Century: Population
• Population growth (2050 – 9.7 billion)
• Per capita consumption growth (up to 3 billion consumers moving from low to
21
th
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
21
th
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?
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
An example: “Green epichlorohydrin”
• Epichlorohydrin’: 2Mt/year (resins, polymers, crosslinker, etc.)
• Petrochemical route
• Surplus of glycerol (from biodiesel production)
• Synthesis from glycerol
What about aromatics?
Drivers:
• Strong growth in global plastics production
• Incentives to green up the BTX business (BTX = benzene, toluene, xylenes)
What about aromatics?
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??
Ex situ catalytic pyrolysis
Pyrolysis
Advantages
• Extended life time of the catalyst
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
Results gram scale unit
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 catalytic pyrolysis
Pyrolysis
• Question: Discuss methods to improve the yield of BTX!
Integrated Cascading Catalytic Pyrolysis (ICCP)
Hypothesis: A (cracking) catalyst could influences both the composition and amount of the gaseous phase.
Integrated Cascading Catalytic Pyrolysis (ICCP)
Recycle higher (reduced) aromatics
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)
Stability of the catalyst
BioPET100
• Drop-in chemicals; purification, separation and modification in existing (petrochemical) infrastructure
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) ……..
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).
