Aqueous phase reforming of the residual waters derived from lignin-rich hydrothermal liquefaction: investigation of representative organic compounds and actual biorefinery streams

Pipitone, Giuseppe; Zoppi, Giulia; Bocchini, Sergio; Rizzo, Andrea Maria; Chiaramonti, David; Pirone, Raffaele; Bensaid, Samir

doi:10.1016/j.cattod.2019.09.040

Cited by 44 publications

(23 citation statements)

References 38 publications

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“…Besides, there are more biomass-based H 2 generation methods also reported in the literature. For instance, Pipitone et al7 investigated APR of residual waters derived from lignin-rich hydrothermal liquefaction. Both model compounds and actual bio-refinery streams were studied.…”

mentioning

confidence: 99%

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Kalekar

Vaidya

2021

Ind. Eng. Chem. Res.

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Wet biomass such as macroalgae (or seaweeds) can be effectively converted into a H 2 -rich gaseous product by catalytic reforming in the liquid phase. Sodium alginate (SA)a major constituent of such biomasswas chosen as the model compound for this study on aqueous-phase reforming (APR). Trials were performed in the 200−230 °C range in a stirred batch reactor for up to 6 h using different alginate concentrations (0.5−2.5 wt %) in aqueous solutions. Low-molecular-weight organic acids such as acetic, propionic, lactic, and succinic acids and gaseous product comprising H 2 , CH 4 , CO, and CO 2 were formed. Contrary to the noncatalytic process, H 2 was selectively produced over commercial 5% Pt/C catalyst for loadings between 2 and 6 kg/m 3 . After 3 h of reaction over Pt/C at T = 225 °C, the values of carbon conversion into gas phase (X) and selectivity to H 2 (S-H 2 ) and H 2 yield (Y-H 2 ) were 9.7, 32.5, and 1.4% respectively. Other noble metals were also tested; however, Pt/C performed better than Ru/C and Pd/C. Several features of Pt/C were investigated using electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and NH 3 -temperature-programmed desorption techniques. A possible reaction scheme for alginate conversion to products was discussed. Despite the low H 2 yield, this work provided the desired starting point for improved macroalgae-to-H 2 conversions via APR.

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mentioning

confidence: 99%

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Kalekar

Vaidya

2021

Ind. Eng. Chem. Res.

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“…For example, we suggested that the presence of the carboxylic group in the hydroxy acid molecule (glycolic acid and lactic acid) firstly led to decarboxylation, that is, C C cleavage as CO 2 ; afterward, the remaining moiety would be similar to methanol and ethanol, and this would lead to more conventional pathways. 34 Looking at the fate of carbon, it can be observed that the carbon to gas conversion decreased from 19% to 13% by adding the carbon balance closed only to 61% and 69%, without and with additive, respectively. It implies that there were important adsorption phenomena on the catalyst surface, which could not be directly quantified through micro-GC and TOC analysis.…”

Section: Influence Of Alkaline Additive On Aprmentioning

confidence: 99%

Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H₂

Fraia¹,

Miliotti²,

Rizzo³

et al. 2022

AIChE Journal

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Lignin-rich stream from lignocellulosic ethanol production was converted into biocrude by continuous hydrothermal liquefaction (HTL) while hydrogen was produced by aqueous phase reforming (APR) of the HTL aqueous by-product. The effects of Na 2 CO 3 and NaOH were investigated both in terms of processability of the feedstock as well as yield and composition of the obtained products. A maximum biocrude yield of 27 wt% was reached in the NaOH-catalyzed runs. A relevant amount of dissolved phenolics were detected in the co-produced aqueous phase (AP), and removed by liquid-liquid extraction using butyl acetate or diethyl ether, preserving the APR catalyst stability and reaching an hydrogen yield up to 146 mmol H 2 L À1 AP. Preliminary mass balances integrating HTL and APR showed that the hydrogen provided by APR may account for up to 46% of the hydrogen amount theoretically required for upgrading the HTL biocrude, thus significantly improving the process performance and sustainability.

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“…Thus, the collection procedure must be carefully considered for adequate comparisons of results as well as for the implementation of these types of procedures in an industrial scale-up perspective. Moreover, the implication of different extraction procedures will impact on possible downstream aqueous phase valorization steps such as aqueous phase reforming [64] or other valorization routes for chemicals extraction [65,66].…”

Section: Compound Distribution Among Htl Fractions: Influence Of Biocmentioning

confidence: 99%

Hydrothermal Depolymerization of Biorefinery Lignin-Rich Streams: Influence of Reaction Conditions and Catalytic Additives on the Organic Monomers Yields in Biocrude and Aqueous Phase

Dell’Orco

Miliotti²,

Lotti³

et al. 2020

Energies

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Hydrothermal depolymerization of lignin-rich streams (LRS) from lignocellulosic ethanol was successfully carried out in a lab-scale batch reactors unit. A partial depolymerization into oligomers and monomers was achieved using subcritical water as reaction medium. The influence of temperature (300–350–370 °C) and time (5–10 minutes) was investigated to identify the optimal condition on the monomers yields in the lighter biocrude (BC1) and aqueous phase (AP) fractions, focusing on specific phenolic classes as well as carboxylic acids and alcohols. The effect of base catalyzed reactions (2–4 wt. % of KOH) was compared to the control tests as well as to acid-catalyzed reactions obtained with a biphasic medium of supercritical carbon dioxide (sCO2) and subcritical water. KOH addition resulted in enhanced overall depolymerization without showing a strong influence on the phenolic generation, whereas sCO2 demonstrated higher phenolic selectivity even though no effect was observed on the overall products mass yields. In conclusion, a comparison between two different biocrude collection procedures was carried out in order to understand how the selected chemical extraction mode influences the distribution of compounds between BC1 and AP.

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Aqueous phase reforming of the residual waters derived from lignin-rich hydrothermal liquefaction: investigation of representative organic compounds and actual biorefinery streams

Cited by 44 publications

References 38 publications

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H₂

Hydrothermal Depolymerization of Biorefinery Lignin-Rich Streams: Influence of Reaction Conditions and Catalytic Additives on the Organic Monomers Yields in Biocrude and Aqueous Phase

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Aqueous phase reforming of the residual waters derived from lignin-rich hydrothermal liquefaction: investigation of representative organic compounds and actual biorefinery streams

Cited by 44 publications

References 38 publications

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Hydrogen Production by Reforming of Sodium Alginate in the Liquid Phase over Pt/C Catalyst

Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H2

Hydrothermal Depolymerization of Biorefinery Lignin-Rich Streams: Influence of Reaction Conditions and Catalytic Additives on the Organic Monomers Yields in Biocrude and Aqueous Phase

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Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H₂