Hydrothermal liquefaction versus catalytic hydrodeoxygenation of a bioethanol production stillage residue to platform chemicals: A comparative study

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Hydrothermal liquefaction versus catalytic

hydrodeoxygenation of a bioethanol production stillage residue to platform chemicals: A comparative study

Item Type Article

Authors Hita, I.;Ghoreishi, S.;Santos, J. I.;Barth, T.;Heeres, H. J.

Citation Hita, I., Ghoreishi, S., Santos, J. I., Barth, T., & Heeres, H. J. (2020). Hydrothermal liquefaction versus catalytic

hydrodeoxygenation of a bioethanol production stillage residue to platform chemicals: A comparative study. Fuel Processing Technology, 106654. doi:10.1016/j.fuproc.2020.106654

Eprint version Post-print

DOI 10.1016/j.fuproc.2020.106654

Publisher Elsevier BV

Journal Fuel Processing Technology

Rights NOTICE: this is the author’s version of a work that was accepted for publication in Fuel Processing Technology. Changes resulting from the publishing process, such as peer review, editing,

corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Fuel Processing Technology, [, , (2020-11-10)] DOI: 10.1016/

creativecommons.org/licenses/by-nc-nd/4.0/

Download date 2023-12-01 20:58:41

Link to Item http://hdl.handle.net/10754/666028

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Supporting information for:

Hydrothermal liquefaction versus catalytic hydrodeoxygenation of a bioethanol production stillage residue to platform chemicals:

a comparative study

I. Hita^a,d*, S. Ghoreishi^b, J.I. Santos^c, T. Barth^b, H.J. Heeres^a*

aChemical Engineering Department, ENTEG, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands

bDepartment of Chemistry, University of Bergen, Allegaten 41, N-5007 Bergen, Norway.

cDepartment of Chemical Engineering, University of the Basque Country (UPV/EHU), PO Box 644- 48080, Bilbao, Spain

dKing Abdullah University of Science and Technology, KAUST Catalysis Center (KCC), Multiscale Reactor Engineering, Thuwal 23955-6900, Saudi Arabia.

* Corresponding authors: [email protected], [email protected]

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Stillage+FA +solvent

Solvolysis Gas

products

Char+adsorbed organic products

Aqueous phase

Filtration

EtAc+THF

Liquid products

Extraction

Char Filtration

Organic products+solvents

Drying, solvent evaporation

Organic products

EtAc+THF

Scheme S1. Schematic overview of hydrothermal liquefaction workup

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BPS/HTL oil + Catalyst

Hydrotreatment Gas

products

Product oil + solids + catalyst

Aqueous

phase Organic oil

Organic products adsorbed on the solids + catalyst

Filtration DCM soluble

products

Acetone soluble products Filtration

Solids

Solids + catalyst DCM

Acetone

Scheme S2. Schematic overview of hydrotreatment workup

FTIR analysis was used to obtain further insights into the structural features of the BPS. The pronounced band at 3334 cm^-1 corresponds to the O-H stretching vibration in aromatic and aliphatic structures, while the band at 2926 cm^-1 is attributable to C-H vibrations in CH2 and CH3 groups. A shoulder at 1710 cm^-1 is also observed, corresponding to C=O bonds in carboxylic acids, conjugated aldehydes or ketones [1,2]. Aromatic skeletal vibrations are present from the bands at 1591, 1507 and 1422 cm^-1. Characteristic guaiacyl (G) unit bands are observed at 1268 and 913 cm^-1, while syringyl (S) unit bands were absent [3,4]. The band at 1163 cm^-1 is assigned to antisymmetric C-O stretching of ester groups, which might be indicative of the presence of ester-linked acids [5]. On the other hand, intense bands corresponding to polysaccharide structures in the 1029-1100 cm^-1 range are also observed, hence proving an important presence of residual (hemi)cellulose material derived from the bioethanol production. Specifically, the highly intense band at 1029 cm^-1 is characteristic of the C-O stretching vibration of cellulose [6].

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4000 3600 3200 2800 2400 2000 1600 1200 800

1055 1029

1455 1422

1507

1710 1591 1268 11631101 913

2926

Wavenumber (cm^-1)

3334

G unit bands

Sugars

Figure S1. FTIR spectra with the most representative bands for the BPS

Table S1. Composition of the gas products (% mol) obtained in the hydrotreatment of the BPS at different conditions

375-Ru 410-Ru 410-Pd 450-Ru 450-Pd

Carbon dioxide 23.8 24.0 24.2 23.6 25.9

Carbon monoxide 1.1 1.9 2.2 1.0 1.7

Ethylene <0.1 <0.1 <0.1 <0.1 <0.1

Ethane 1.5 2.4 2.5 3.8 4.4

Propylene <0.1 <0.1 <0.1 <0.1 <0.1

Propane 0.9 1.4 1.5 2.2 2.0

Methane 28.2 17.6 10.0 30.0 14.8

Hydrogen 44.6 52.8 59.5 39.5 51.1

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Table S2. Elemental composition (%) of the BPS residue, direct HDO organic products, liquified oils from HTL and the oils upgraded through the 2-step HTL-HDO approach

Oxygen removal (%)

C H O N S From BPS From HTL oil

BPS 47.9 5.2 46.3 0.6 <0.01

Oils from direct HDO of BPS

375-Ru 84.2 8.4 6.3 1.1 <0.01 86.4

410-Ru 85.0 8.6 5.5 1.1 <0.01 88.2

410-Pd 85.2 8.3 5.4 1.0 <0.01 88.3

450-Ru 85.2 9.2 4.3 1.2 <0.01 90.7

450-Pd 86.1 9.4 3.9 0.6 <0.01 91.7

Liquified oils from HTL

HTL1 69.3 7.3 22.9 0.5 <0.01 50.6

HTL2 75.6 7.9 15.8 0.7 <0.01 65.9

HDO-upgraded products from the HTL1 oil

410-Ru 84.4 9.0 6.2 0.4 <0.01 73.1

410-Pd 84.3 9.3 5.9 0.5 <0.01 74.5

450-Ru 84.9 8.3 6.4 0.5 <0.01 72.1

450-Pd 78.0 8.6 6.0 0.4 <0.01 73.8

HDO-upgraded products from the HTL2 oil

375-Ru 83.2 9.3 7.2 0.3 <0.01 54.4

410-Ru 84.5 9.0 6.1 0.5 <0.01 61.4

410-Pd 84.7 9.3 5.5 0.6 <0.01 65.5

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Figure S2. GCxGC-FID chromatogram of typical lignin-derived oil, where compuds are classified on a chemical nature criteria as: (1) cyclic alkanes, (2) linear alkanes, (3) aromatics, (4) ketones, (5) naphthalenes, (6) guaiacols, (7) alkylphenolics and (8) catechols.

100 1000 10000

0.0 0.2 0.4 0.6 0.8 1.0

220-240 g mol^-1 290-310 g mol^-1

GC detectables

Relative RID Intensity

Molecular weight (g mol^-1)

375 - Ru 410 - Ru 410 - Pd 450 - Ru 450 - Pd 430 g mol^-1

Figure S3. Molecular weight distributions of the oils obtained from the direct hydrotreatment of the BPS

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100 1000 10000 0.0

0.2 0.4 0.6 0.8 1.0

Relative RID intensity

Molecular weight (g mol^-1)

HTL1 410-Ru 410-Pd 450-Ru 450-Pd HTL2 375-Ru 410-Ru 410-Pd

GC detectables

840 g mol^-1 420 g mol^-1

310 g mol^-1

240-270 g mol^-1 210-220 g mol^-1

Figure S4. Molecular weight distributions of the oils obtained from the hydrotreatment of the HTL oils derived from the BPS.

Figure S5. ¹³C NMR spectra for the HTL oils

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