Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/ δ - Al 2 O 3 catalysts

1. Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/δ-Al2O3 catalysts Agnes Ardiyanti1, Sofia Khromova2, Robbie Venderbosch3, Vadim Yakovlev2, Erik Heeres1 1University of Groningen, Groningen, The Netherlands 2Boreskov Institute of Catalysis, Novosibirsk, Russia 3BTG Biomass Technology Group, Enschede, The Netherlands

2. Introduction Lignocellulosic biomass Existing refinery Catalyst, H2 Pyrolysis (+ VGO) Upgraded oil (low O) Pyrolysis oil (high O) Catalytic Hydrotreatment P, T

3. Novel hydrotreatment catalysts • Catalyst requirement • strong hydrogenation activity • stable at hydrotreatment condition (aqueous, acidic) • Conventional catalysts • sulfided NiCu or CoMo on γ-Al2O3 • leaching and sulfur contamination • Novel NiCu/δ-Al2O3 catalysts • Developed by BIC • Cu as reduction aid • δ-Al2O3 is more stable than γ-Al2O3

4. Approach • Catalyst testing • HDO of Anisole • Hydrotreatment of pyrolysis oil • Catalyst characterisation • TPR, XRD, ICP • Various catalyst compositions

5. HDO of Anisole (1) Mechanism1 Flow reactor (BIC) desired products

6. HDO of Anisole (2) • Yield of oxygen-free products 16Ni2Cu gives the highest HDO yield

7. XRD analysis • No Ni(0) was found at 20.8Ni after reduction at 300 oC (reduction temperature of Ni is > 500 oC) • Ni(0) was formed on 13.8Ni6.83Cu after reduction 13.8Ni6.83Cu Ni 20.8Ni NiO Cu does not have HDO activity, but supports the reduction of Ni Reduction was performed at 300 oC and 10 bar of H2

8. Hydrotreatment of pyrolysis oil • Reactor: 100 ml autoclave, in-situ catalyst reduction possible • Feed: pine pyrolysis oil (provided by VTT, Finland) • Condition: 150 oC (1h), 350 oC (3h), pressure 200 bar at 350 oC. • 25 g pyrolysis oil and 1.25 g (5 wt%) of catalyst was used Autoclave (RuG)

9. Upgraded oil Phase separation occurred Deoxygenation, even without catalyst  Not the only criterium!

10. Hydrogenation activities • Van Krevelen plot is used to calculate the hydrogenation activities, blank experiment as the reference 16Ni2Cu and 13.8Ni6.83Cu are the most active

11. Upgraded oil – physical properties • TGA and GPC analyses 16Ni2Cu and 13.8Ni6.83Cu give products with the best physical properties

12. HRTEM Fresh 16.8Ni6.83Cu Spent 16.8Ni6.83Cu Active metal particle size: 10 nm (fresh)  100 nm (spent). ICP showed leaching of Ni, Cu, and Al Dissolution and recrystallisation of NiCu seem to occur

13. Conclusions • Non-sulfided Ni-based catalysts have been developed and tested. • NiCu catalysts are active in HDO of anisole. • Cu is not active, but supports the reduction of Ni at lower temperature (300 oC). • NiCu catalysts are active in hydrotreatment of pyrolysis oil. • Most active catalysts: 16Ni2Cu and 18.6Ni6.83Cu (highest hydrogenation activity, lowest products Mw and TG residue). • Catalyst stability is not optimal (improvement of the catalysts stability is in progress).

14. UIC Thank you! Boreskov Institute of Catalysis – SB RAS Financial support: