High-volume chemicals from biomass André Heeres, August 2018

Content

• Introduction (drivers for bio-based chemicals)

• Strategies for conversion

• An example: bio-aromatics

• Thermochemical conversions

• Downstream to plastics

• Conclusions

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

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

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)

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

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

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

Drop in chemicals/Novel chemicals

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.)

Drop in chemicals from bioethanol

What about aromatics?

Drivers:

• Strong growth in global

plastics production

• Incentives to green up the

BTX business (BTX =

benzene, toluene, xylenes)

• Drop-in chemicals

What about aromatics?

• Huge markets!

Competition

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.

Ex situ catalytic pyrolysis

Pyrolysis

Advantages

• Extended life time of the catalyst

• Ability to use highly contaminated/wet biomass streams

Mechanism

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

Results gram scale unitEx situ aromatization, T = 565 ⁰C, H-ZSM-5 (23); 0.3-0.5 mm, cat : biomass = 3:1

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

GC analysis

Ex situ catalytic pyrolysis

Pyrolysis

• Question: Discuss methods to improve the yield of BTX!

- Groups, 5-10 minutes

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.

Integrated Cascading Catalytic Pyrolysis (ICCP)

TMR; pinewood : pyrolysis catalyst : (H-ZSM-5 (23) = 1 : 1 : 80, T1 = 550 ⁰C, T2 = 575 ⁰C)

Recycle higher (reduced) aromatics

Co-feeding with PAH: slightly higher yields

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!

Stability of the catalyst

• H-ZSM-5 (23) ex-situ pyrolysis with intermediate oxidative catalyst regeneration (black liquor).

Downstream: Towards green plastics

BioPET100

• Drop-in chemicals; purification, separation and modification in existing (petrochemical) infrastructure

• Initial focus on p-terephthalic acid (PTA) and iso-phthalic acid (IPA)

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).

• Downstream processing afforded fully sustainable BioPET100.