Novel Ni-based catalysts for the hydrotreatment of fast pyrolysis liquids

Transcription

1 Novel Ni-based catalysts for the hydrotreatment of fast pyrolysis liquids Agnes Ardiyanti, Arjan Kloekhorst, Y. Wang, Erik Heeres (University of Groningen) Robbie Venderbosch (BTG)

2 Date Content Introduction Catalytic hydrotreatment Objectives Results and discussion - Identification of novel catalysts - Process studies in continueous set-ups Conclusions Acknowledgment

3 Pyrolysis 2.0:

4 Catalytic hydrotreatment H 2 Fast pyrolysis liquids or fractions Catalyst, P, T Gas Upgraded Oil Water - CH x O y - + c H 2 - CH x - + (H 2 O, CO 2, CH 4, CO) Typical conditions: o C, up to 200 bar

5 Two stage hydrotreatment Pyrolysis liquids Stabilisation Picula catalysts SPO Deep Hydrodeoxygenation CPO Albemarle Specialty HDO catalyst Refining Mixed transportation Fuels (MTF) Co-feeding in refinery

6 Objectives hydrotreatment Process considerations: Low H 2 consumption High C yield Low CH 4 yield Low CO 2 (CO) yield Active, stable and cheap catalysts low temperature and pressure Product considerations Reduced oxygen content, exact amount depending on product application Low viscosity Low water content Low coking tendency (improved thermal stability) Preferably miscible with hydrocarbons

7 Stabilisation: catalyst developments Benchmark: Ru/C Bimetallic noble metal catalysts a Ni-Cu catalyst on supports b,c Improved Ni-Cu catalysts (Picula) d a. A.R. Ardiyanti, A. Gutierrez, M Honkela. O. Krause, H.J. Heeres, Applied Catalyis A 407(1-2) (2011) b. A.R. Ardiyanti, S.A. Khromova, R.H. Venderbosch,V.A. Yakovlev, I.V. Melián-Cabrera, H.J. Heeres, Applied Catalysis A 449 (2012) c. A.R. Ardiyanti, S.A. Khromova, R.H. Venderbosch, V.A. Yakovlev, H.J. Heeres, Applied Catalysis B: Environmental (2012) d. Venderbosch and Heeres; Chapter 17: Pyrolysis Oil Stabilisation by Catalytic Hydrotreatment, Biofuel's Engineering Process Technology, Free download: Patent application pending

8 Picula catalysts Catalyst Active metal loading Support (wt%) Picula Cat B Ni: 58.3; Pd: 0.7 Silica Picula Cat C Ni: 28.8; Cu: 3.7 Silica, kaolin Picula Cat D Ni: 57.9; Cu: 7 Silica Picula Cat E Ni: 36.5; Cu: 2.3 Silica, zirconia, lanthanumoxide High Ni content (29-58 wt%) Promoted with Cu, Pd Various supports Prepared by BIC Venderbosch and Heeres; Chapter 17: Pyrolysis Oil Stabilisation by Catalytic Hydrotreatment, Biofuel's Engineering Process Technology, Free download: Venderbosch and Heeres et al., 2010, Stabilization of biomass-derived pyrolysis oil, J. of Chem. Techn. & Biotech., 85(5),

9 Batch studies Picula Conditions: 150 C, 1 h 350 C, 3 h 200 bar Methanation!

10 Batch studies

11 Continuous experiments 4 packed-beds in series Picula catalyst H 2 pressure: 200 bar WHSV = h -1 Variable: T Analyses: CHN, TGA, GPC, TAN, CAN, 2D-GC

12 Molecular weight (GPC) 12 Sequence: Limited (thermal) polymerisation till 250 o C (Hydro)-cracking above C

13 Total acid number 13 Acids are very persistent, reactive only above C

14 Elemental composition Pyrolysis oil +H 250 C 150 C Sequence: Hydrogenation Dehydration Hydrogenation - water 320 C 350 C +H 400 C

15 Deep deoxygenation Pyrolysis liquids Stabilisation Picula catalysts SPO Deep Hydrodeoxygenation CPO Albemarle Specialty HDO catalyst Refining Mixed transportation Fuels (MTF) Co-feeding in refinery Marsman, J.H.; Wildschut, J.; Evers, P.; Koning, S. de; Heeres, H.J. Identification and classification of components in flash pyrolysis oil and hydrodeoxygenated oils by two-dimensional gas chromatography and time-of-flight mass spectrometry Journal of Chromatography A, 1188 (2008) 17 25

16 From PL to MTF Picula catalyst followed by Albemarle Specialty HDO catalyst

17 Elemental compositions Elemental analysis: sequence of hydrogenation, dehydration and hydrogenation

18 2D GC analyses

19 Visual appearance

20 Conclusions Novel catalysts for pyrolysis oil stabilisation by catalytic hydrotreatment have been identified Picula catalysts show unique performance Improved product properties at low processing temperature - Low hydrogen consumptions due to limited methane formation - Good hydrothermal stability (run times up to 400 h have been demonstrated) Two stage hydrotreatment leads to deep deoxygenation and formation of hydrocarbons (mix of transportation fuels)

21 Acknowledgement Sofia Khromova, Maria Bykova, Vadim Yakovlev (BIC)