The Thermal and Catalytic Sciences Symposium 2018

Co-feeding of reduced poly-aromatics to the catalytic

pyrolysis of biomass: Improved yields of BioBTX

André Heeres, PhD

• BioBTX, Zernikelaan 17, 9747 AA Groningen, The Netherlands

• University of Groningen, Nijenborgh 4 9747 AG Groningen, The Netherlands

• Hanze University of Applied Sciences, Zernikeplein 7, 9747 AS Groningen

Content

• “Drivers for bio-aromatics”

• Catalytic pyrolysis towards aromatics/BTX

• H/C_eff ratio of feedstocks used in catalytic pyrolysis, influence on yield of BTX

• Valorization of the higher aromatic fraction (co-feeding)

• Downstream to polyesters

20

_{Century: The great acceleration}

• Annual extraction growth

- construction materials 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

21

_{Century: Population}

• Per capita consumption growth (up to 3 billion consumers moving from low to middle class consumption till 2030)

• Increased need materials

Plastics from biomass

• Sustainable Consumption and Production, utilization of natural resources: an attractive alternative?

• About 40% of plastics contain aromatics.

(Bio)aromatics: applications

Prices BTX strongly dependent on oil price (benzene $900/ton, toluene $800/ton, p-xylene $1050/ton (oil about $60 barrel))

7

Catalytic pyrolysis towards aromatics/BTX

In situ catalytic pyrolysis

• Efficient one-step process

• Sustainable, low carbon footprint

• Non food and cheap biomass

• Conventional zeolite catalysts

• Moderate yields of BTX (5-25%, depending on biomass/conditions)

• …….. but the “life time” of the catalyst??

Ex situ aromatization

• Extended life time of the catalyst

• Ability to use highly contaminated/wet biomass streams

• More “tools” for optimization

1. Thermal cracking 2. Catalytic conversion 3. Liquids collection

Ex situ catalytic pyrolysis Black Liquor

• Tandem Micro reactor (T₁ = 500°C, T₂ = 600°C)

André Heeres, Niels Schenk, Inouk Muizebelt, Ricardo Blees, Bart De Waele, Arend-Jan Zeeuw, Nathalie Meyer, Rob Carr, Erwin Wilbers, Hero Jan Heeres,

ACS Sustainable Chem. Eng., 2018, 6 (3), pp 3472–3480

Integrated Cascading Catalytic Pyrolysis (ICCP)

Hypothesis: A (cracking) catalyst could influence 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

1. Thermal cracking 2. Catalytic conversion 3. Liquids collection

Significant effects “cracking” catalyst on yields BTX

High H/C

increase yields BTX

• Glucose, sorbitol, glycerol, tetrahydrofuran, methanol, several bio-oils (fixed bed, H-ZSM-5 catalyst)

H. Zhang, Y-T Cheng, T.P. Vispute, R. Xiao, G.W. Huber, Energy Environ. Sci, 2011, 2297.

• An example (glycerol, C₃H₈O₃)

• H/C_eff= (8-2*3)/3 = 2/3 = 0,667

• Increasing H/C_eff results in higher BTX yields and lower coke yields.

Ex situ pyrolysis: product distribution

source BTX yield (%) bio-oil (%) ratio

glycerol 15.48 33.46 2.16 sucrose 3.82 13.71 3.59 cellulose 4.48 13.95 3.11 jatropha oil 23.71 53.34 2.25 lignin 2.14 12.19 5.70 wood 3.02 16.03 5.30 Gram scale unit, H-ZSM-5 (23), T = 550 ⁰C

S. He, I. Muizebelt, A. Heeres, N.J. Schenk, R. Blees, H.J. Heeres, Appl. Cat. B: Environmental, 2018, 45-55.

“Reduced polyaromatic hydrocarbons”

• Distillation (isolation BTX)

• (Partial) hydrogenation of higher aromatics obtained

“Reduced polyaromatic hydrocarbons”

• Utilization as a hydrogen rich additive in co-pyrolysis of biomass feedstocks.

• Additional formation of BTX from biomass.

•

%C = 88,45%, %H = 11,55%

•

“C

H

”

Co-feeding with biomass:

additional formation of BTX

• Ex situ pyrolysis of several biomass feedstocks co-fed with reduced PAH (i.e., PCA) at

1:1 wt. ratio using H-ZSM-5 zeolite

Conclusions

•

Sustainable raw materials are an attractive alternative for the

synthesis of high volume chemicals, including aromatics.

•

BioBTX and the University of Groningen have developed novel

strategies in order to increase the yields of bioaromatics from

biomass.

•

The preparation of sustainable plastics was demonstrated with

BioPET100.

Acknowledgement