|Date Catalytic Hydrotreatment of Pyrolysis Oil with NiCu/δ-Al 2 O 3 catalysts Agnes Ardiyanti 1, Sofia Khromova 2, Robbie Venderbosch 3, Vadim Yakovlev 2, Erik Heeres 1 1 University of Groningen, Groningen, The Netherlands 2 Boreskov Institute of Catalysis, Novosibirsk, Russia 3 BTG Biomass Technology Group, Enschede, The Netherlands

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

|Date Novel hydrotreatment catalysts Catalyst requirement strong hydrogenation activity stable at hydrotreatment condition (aqueous, acidic) Conventional catalysts sulfided NiCu or CoMo on γ-Al 2 O 3 leaching and sulfur contamination Novel NiCu/δ-Al 2 O 3 catalysts Developed by BIC Cu as reduction aid δ-Al 2 O 3 is more stable than γ-Al 2 O 3

|Date Approach ›Various catalyst compositions CatalystNi (wt%) Cu (wt%) 24.5Cu Ni18.2Cu Ni11.8Cu Ni6.83Cu Ni2Cu Ni20.8- ›Catalyst testing  HDO of Anisole  Hydrotreatment of pyrolysis oil ›Catalyst characterisation  TPR, XRD, ICP

|Date HDO of Anisole (1) Flow reactor (BIC)Mechanism 1 desired products

|Date HDO of Anisole (2) ›Yield of oxygen-free products 16Ni2Cu gives the highest HDO yield

|Date XRD analysis 13.8Ni6.83Cu 20.8Ni NiO Ni No Ni(0) was found at 20.8Ni after reduction at 300 o C (reduction temperature of Ni is > 500 o C) Ni(0) was formed on 13.8Ni6.83Cu after reduction Cu does not have HDO activity, but supports the reduction of Ni Reduction was performed at 300 o C and 10 bar of H 2

|Date Hydrotreatment of pyrolysis oil Reactor: 100 ml autoclave, in-situ catalyst reduction possible Feed: pine pyrolysis oil (provided by VTT, Finland) Condition: 150 o C (1h), 350 o C (3h), pressure 200 bar at 350 o C. 25 g pyrolysis oil and 1.25 g (5 wt%) of catalyst was used Pyrolysis oil composition C (wt%)40.1 H (wt%)7.6 O (wt%)52.1 Moisture (wt%)23.9 Autoclave (RuG)

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

|Date 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

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

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

|Date 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 o C). ›NiCu catalysts are active in hydrotreatment of pyrolysis oil. ›Most active catalysts: 16Ni2Cu and 18.6Ni6.83Cu (highest hydrogenation activity, lowest products M w and TG residue). ›Catalyst stability is not optimal (improvement of the catalysts stability is in progress).

|Date Thank you! UIC Boreskov Institute of Catalysis – SB RAS Financial support: