On the selective desulphurization of biomass derivatives in supercritical water

Baudouin, David; Xiang, Haige; Vogel, Frédéric

doi:10.1016/j.biombioe.2022.106529

Cited by 5 publications

(6 citation statements)

References 49 publications

(74 reference statements)

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“…More specifically, ZnO, Fe 3 O 4 , Cu 2 O, MnO and CeO 2 were the dominating crystalline phases in the fresh ZnO/C, FeO x /C, CuO x /C, MnO x /C, and CeO x /C, respectively, and did not suffer from reduction/oxidation during reductive HTG reaction. The spent MO x /C all show crystalline metal-sulfide phases with the exception of FeO x /C, which is in line with the very limited S-absorption performance of iron described in an earlier work 19 . In spent MO x /C (M = Zn, Cu, Mn, and Ce), crystalline sulfides are formed as ZnS, Cu 1.8 S, MnS, and Ce 2 S 3 , respectively, revealing the theoretical S-absorption capacity of those materials.…”

Section: Resultssupporting

confidence: 88%

“…These observations further confirm the poor ability of iron oxide to absorb sulfur. This is due to the lack of stability of iron sulfide in supercritical water previously reported 19 , 58 . This finding also discloses the high stability of the oxide with limited coarsening/sintering in SCW conditions.…”

Section: Resultsmentioning

confidence: 93%

“…Without using S-absorbent, the spent liquid was mainly composed of 60 µmol S ethanethiol and 15 µmol S DEDS. Note that the DEDS observed might be formed back from ethyl thiyl radicals during the quenching of the reactor, or from ethanethiol after sampling 19 . Other compounds such as isopropyl disulfide ((CH 3 ) 2 CHSSCH(CH 3 ) 2 ), methyl ethyl trisulfide (CH 3 SSSC 2 H 5 ), and diethyl trisulfide (C 2 H 5 SSSC 2 H 5 ) might also have been formed from corresponding radicals present in the supercritical fluid or from the corresponding thiols and H 2 S after sampling.…”

Section: Resultsmentioning

confidence: 99%

“…Aside from oxides, carbon is one of the few materials that show long-term stability of its porous framework and particle integrity under SCW 9 , 17 , 18 , making it a promising low-cost binder material for such conditions. Apart from ZnO, the oxides of molybdenum (Mo), manganese (Mn), and cerium (Ce) also showed good sulfur absorption capacity with intermediate activity in decreasing organosulfur concentration, and Cu(0) demonstrated outstanding performance for both desulfurization and S-absorption 2 , 19 – 21 . It is therefore expected that a composite of porous carbon and high loading of metal (or metal oxides) will be an ideal S-absorbent, showing both high S-absorption capacity and structural stability under SCW.…”

Section: Introductionmentioning

confidence: 99%

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Metal oxide nanoparticles embedded in porous carbon for sulfur absorption under hydrothermal conditions

Xiang

Baudouin

Vogel

2023

Sci Rep

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MOx (M = Zn, Cu, Mn, Fe, Ce) nanoparticles (NPs) embedded in porous C with uniform diameter and dispersion were synthesized, with potential application as S-absorbents to protect catalysts from S-poisoning in catalytic hydrothermal gasification (cHTG) of biomass. S-absorption performance of MOx/C was evaluated by reacting the materials with diethyl disulfide at HTG conditions (450 °C, 30 MPa, 15 min). Their S-absorption capacity followed the order CuOx/C > CeOx/C ≈ ZnO/C > MnOx/C > FeOx/C. S was absorbed in the first four through the formation of Cu1.8S, Ce2S3, ZnS, and MnS, respectively, with a capacity of 0.17, 0.12, 0.11, and 0.09 molS molM−1. The structure of MOx/C (M = Zn, Cu, Mn) evolved significantly during S-absorption reaction, with the formation of larger agglomerates and separation of MOx particles from porous C. The formation of ZnS NPs and their aggregation in place of hexagonal ZnO crystals indicate a dissolution/precipitation mechanism. Note that aggregated ZnS NPs barely sinter under these conditions. Cu(0) showed a preferential sulfidation over Cu2O, the sulfidation of the latter seemingly following the same mechanism as for ZnO. In contrast, FeOx/C and CeOx/C showed remarkable structural stability with their NPs well-dispersed within the C matrix after reaction. MOx dissolution in water (from liquid to supercritical state) was modeled and a correlation between solubility and particle growth was found, comforting the hypothesis of the importance of an Ostwald ripening mechanism. CeOx/C with high structural stability and promising S-absorption capacity was suggested as a promising bulk absorbent for sulfides in cHTG of biomass.

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Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Metal oxide nanoparticles embedded in porous carbon for sulfur absorption under hydrothermal conditions

Xiang

Baudouin

Vogel

2023

Sci Rep

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“…This may be due to the (hydro)thermal instability of the S–S bond by homolytic dissociation, whereas in the case of DMS, the C–S bonds need higher temperatures to be cleaved, typically beyond the critical point of water where methyl radical formation is favored . Note however that disulfides can form from the condensation of two thiols . In the following course, both concentrations vary between 5 and 20 mg·L –1 with the exception of the DMTS concentration at T R = 350 °C.…”

Section: Resultsmentioning

confidence: 99%

The Impact of Sulfur-Containing Inorganic Compounds during the Depolymerization of Lignin by Hydrothermal Liquefaction of Black Liquor

Wörner,

Werner,

Hornung

et al. 2024

Energy Fuels

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Lignin is a promising resource for the sustainable production of platform chemicals and biofuels. The paper industry produces large quantities of lignin every year, mostly dissolved in a black liquor. With the help of hydrothermal liquefaction, black liquor can be used directly as a feedstock to depolymerize the lignin to desired products. However, because various cooking chemicals (e.g., NaHS, NaOH) used in the Kraft process, dominant in the paper industry, are also dissolved in the black liquor, it is necessary to study in detail their influence on the process as well as their fate. In this work, the focus was on the fate of sulfur and the influence of sulfide (HS − ). For this purpose, hydrothermal liquefaction experiments (250−400 °C) were carried out with black liquor and self-prepared model black liquor with different sulfide concentrations (0−3 g•L −1 HS − ) in batch reactors (V = 25 mL), and the products were analyzed to understand the chemical pathways involving sulfur. It was found that the inorganic sulfur compounds react with organic matter to produce organic sulfur compounds. Dimethyl sulfide is the most abundant of these products. The HS − concentration correlates with the amount of dimethyl sulfide produced. Because methanethiol has also been qualitatively detected, the reaction mechanism of Karnofski et al. for the formation of dimethyl sulfide in the Kraft process also applies to the hydrothermal liquefaction of black liquor. Increased sulfide concentration in the feed leads to an accelerated depolymerization of lignin. In contrast, the yields of some aromatic monomers decrease slightly, possibly as a result of repolymerization reactions also occurring more quickly.

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The effect of Ni- and Mo-based materials on thermochemical sulfate reduction by glycerol under hydrothermal process conditions

Chang,

Vogel,

Kröcher

et al. 2024

Chemical Engineering Research and Design

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On the selective desulphurization of biomass derivatives in supercritical water

Cited by 5 publications

References 49 publications

Metal oxide nanoparticles embedded in porous carbon for sulfur absorption under hydrothermal conditions

Metal oxide nanoparticles embedded in porous carbon for sulfur absorption under hydrothermal conditions

The Impact of Sulfur-Containing Inorganic Compounds during the Depolymerization of Lignin by Hydrothermal Liquefaction of Black Liquor

The effect of Ni- and Mo-based materials on thermochemical sulfate reduction by glycerol under hydrothermal process conditions

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