TY - JOUR

T1 - Catalytic hydrotreatment of the pyrolytic sugar and pyrolytic lignin fractions of fast pyrolysis liquids using nickel based catalysts

AU - Yin, Wang

AU - Alekseeva, Maria V.

AU - Venderbosch, Robertus Hendrikus

AU - Yakovlev, Vadim A.

AU - Heeres, Hero Jan

N1 - Publisher Copyright: © 2020 by the authors. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/1/6

Y1 - 2020/1/6

N2 - Catalytic hydrotreatment is recognized as an efficient method to improve the properties of pyrolysis liquids (PO) to allow co-feeding with fossil fuels in conventional refinery units. The promising catalyst recipes identified so far are catalysts with high nickel contents (38 to 57 wt.%), promoted by Cu, Pd, Mo and/or a combination, and supported by SiO2, SiO2-ZrO2, SiO2-ZrO2-La2O3 or SiO2-Al2O3. To gain insights into the reactivity of the pyrolytic sugar (PS) and pyrolytic lignin (PL) fraction of PO, hydrotreatment studies (350 °C, 120 bar H2 pressure (RT) for 4 h) were performed in a batch autoclave. Catalyst performance was evaluated by considering the product properties (H/C ratio, the charring tendency (TGA) and molecular weight distribution (GPC)) and the results were compared with a benchmark Ru/C catalyst. All Ni based catalysts gave products oils with a higher H/C compared to Ru/C. The Mo promoted catalyst performed best, giving a product with the highest H/C ratio (1.54) and the lowest TG residue (0.8 wt.% compared to 12 wt.% for the fresh PS). The results further revealed that the PS fraction is highly reactive and full conversion was achieved at 350 °C. In contrast, the PL fraction was rather inert, and only part of the PL fraction was converted. The fresh and spent catalysts after the hydrotreatment of the PS and PL fractions were characterized by elemental analysis, powder X-Ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM-EDX). The results revealed that the use of PS as the feed leads to higher amounts of coke deposits on the catalysts, and higher levels of Ni agglomeration when compared to experiments with PL and pure PO. This proofs that proper catalyst selection for the PS fraction is of higher importance than for the PL fraction. The Mo promoted Ni catalysts showed the lowest amount of coke and the lowest tendency for Ni nanoparticle agglomeration compared to the monometallic Ni and bimetallic Ni-Cu catalysts.

AB - Catalytic hydrotreatment is recognized as an efficient method to improve the properties of pyrolysis liquids (PO) to allow co-feeding with fossil fuels in conventional refinery units. The promising catalyst recipes identified so far are catalysts with high nickel contents (38 to 57 wt.%), promoted by Cu, Pd, Mo and/or a combination, and supported by SiO2, SiO2-ZrO2, SiO2-ZrO2-La2O3 or SiO2-Al2O3. To gain insights into the reactivity of the pyrolytic sugar (PS) and pyrolytic lignin (PL) fraction of PO, hydrotreatment studies (350 °C, 120 bar H2 pressure (RT) for 4 h) were performed in a batch autoclave. Catalyst performance was evaluated by considering the product properties (H/C ratio, the charring tendency (TGA) and molecular weight distribution (GPC)) and the results were compared with a benchmark Ru/C catalyst. All Ni based catalysts gave products oils with a higher H/C compared to Ru/C. The Mo promoted catalyst performed best, giving a product with the highest H/C ratio (1.54) and the lowest TG residue (0.8 wt.% compared to 12 wt.% for the fresh PS). The results further revealed that the PS fraction is highly reactive and full conversion was achieved at 350 °C. In contrast, the PL fraction was rather inert, and only part of the PL fraction was converted. The fresh and spent catalysts after the hydrotreatment of the PS and PL fractions were characterized by elemental analysis, powder X-Ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM-EDX). The results revealed that the use of PS as the feed leads to higher amounts of coke deposits on the catalysts, and higher levels of Ni agglomeration when compared to experiments with PL and pure PO. This proofs that proper catalyst selection for the PS fraction is of higher importance than for the PL fraction. The Mo promoted Ni catalysts showed the lowest amount of coke and the lowest tendency for Ni nanoparticle agglomeration compared to the monometallic Ni and bimetallic Ni-Cu catalysts.

KW - Catalytic hydrotreatment

KW - Nickel-based catalysts

KW - Pyrolysis liquids

KW - Pyrolytic lignin

KW - Pyrolytic sugars

KW - catalytic hydrotreatment

KW - HYDROLYSIS

KW - MODEL

KW - nickel-based catalysts

KW - IDENTIFICATION

KW - LEVOGLUCOSAN

KW - HEAVY FRACTION

KW - pyrolytic lignin

KW - HYDRODEOXYGENATION

KW - pyrolytic sugars

KW - BIO-OIL

KW - BIOMASS

KW - pyrolysis liquids

KW - 2-DIMENSIONAL GAS-CHROMATOGRAPHY

KW - AMORPHOUS CATALYSTS

UR - http://www.scopus.com/inward/record.url?scp=85078008383&partnerID=8YFLogxK

U2 - 10.3390/en13010285

DO - 10.3390/en13010285

M3 - Article

AN - SCOPUS:85078008383

VL - 13

JO - Energies

JF - Energies

SN - 1996-1073

IS - 1

M1 - 285

ER -