Hydrothermal conversion of carbohydrate biomass into formic acid at mild temperatures

Jin, Fangming; Yun, Jimmy; Li, Guang Ming; Kishita, Atsushi; Tohji, Kazuyuki; Enomoto, Heiji

doi:10.1039/b802076k

Cited by 234 publications

(185 citation statements)

References 19 publications

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“…Therein, the biomass is oxidized by polyoxometalates to FA and consecutively to formaldehyde in an aqueous solution under solar irradiation applying very mild conditions avoiding thermal degradation. 11 The first study aiming at a selective synthesis of FA or formate salts from biomass was published in 2008 by Jin et al 12,13 Glucose, a model compound for carbohydrate biomass, was oxidised hydrothermally with hydrogen peroxide as the oxidant at temperatures between 473 K and 573 K in the presence of alkali hydroxide, which obtained FA in up to 75% yield. However, such high FA yields were only obtained at high alkali concentrations (1.2 M) and using over-stoichiometric use of H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Reichert

Brunner

Jess

et al. 2015

Energy Environ. Sci.

135

139

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a Herein, we report a remarkable finding that biomass oxidation to formic acid (FA) in water-organic biphasic reaction systems is far more selective than the same reaction in a monophasic aqueous media.While literature claims that the yield of FA from carbohydrates and biomass is limited to less than 68%, even for simple substrates such as glucose or glycerol, we demonstrate in this study that FA yields of up to 85% can be obtained from glucose. Using our biphasic reaction protocol, even raw lignocellulosic biomass, such as beech wood, leads to FA yields of 61%. This is realized by applying polyoxometalate H 8 PV 5 Mo 7 O 40 as a homogeneous catalyst, oxygen as the oxidant and water as the solvent in the presence of a long-chain primary alcohol as an in-situ extracting agent. The new, liquid-liquid biphasic operation opens a highly effective way to produce pure FA, a liquid syngas equivalent, from wood in a robust, integrated, and low-temperature process.

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Section: Introductionmentioning

confidence: 99%

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Reichert

Brunner

Jess

et al. 2015

Energy Environ. Sci.

135

139

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“…The pH of the liquid residuals were 7.88 for LA, 2.18 for LB and 2.15 for LN; these pH values indicate that both neutral and Nb 2 O 5 pre-processing routes produced acidic liquid residuals, which could result from the presence of simple organic acids such as acetic and lactic acids [12,[31][32][33]. The liquid residual LA, from the alkaline preprocessing appeared darker and contained more carbon than those from either the Nb 2 O 5 or neutral pre-processing, according to TOC results.…”

Section: Products From Sawdust Pre-processingmentioning

confidence: 99%

“…Onwudili and Williams [10][11], in a one-stage direct process, also suggested that sodium hydroxide was able to degrade different types of biomass, producing biomass-alkali liquor that was suitable for hydrothermal gasification, yielding mainly hydrogen and some methane. Jin et al [12] also demonstrated the potential of producing chemicals such as acetic and formic acids via alkaline hydrothermal biomass processing. In addition, many researchers have investigated the supercritical water gasification of waste biomass liquor from various biomass-based industries [13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Enhanced methane and hydrogen yields from catalytic supercritical water gasification of pine wood sawdust via pre-processing in subcritical water

Onwudili

Williams

2013

RSC Adv.

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A two-stage batch hydrothermal process has been investigated with the aim of enhancing the yields of hydrogen and methane from sawdust. Samples of the sawdust were rapidly treated in subcritical water and with added Na 2 CO 3 (alkaline compound) and Nb 2 O 3 (solid acid) at 280 °C, 8 MPa. Each pre-processing route resulted in a solid recovered product (SRP), an aqueous residual and a small amount of gas composed mainly of CO 2 . In the second stage, the SRP and the liquid residuals were gasified in supercritical water in the presence of Ru/Al 2 O 3 catalyst for reaction times of up to 60 min for the SRP at 500 °C, 30 MPa. With the catalyst, carbon gasification efficiencies and methane selectivity increased with increasing reaction time. Overall, SRP from the Na 2 CO 3 pre-processing route produced 51% more hydrogen and 61% more methane than the original sawdust under identical reaction conditions. The cumulative yields of methane and hydrogen were 57.1 mol/kg, 42.5 mol/kg and 47.7 mol/kg, from Na 2 CO 3 , Nb 2 O 5 and neutral pre-processing routes, respectively. The combined yield of the two gases from direct SCWG of the original sawdust was 24.6 mol/kg. The entire process may re-present a stepchange in future energy production from biomass as the products from the first stage can be used as feedstocks for various other biomass conversion technologies.

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“…Thus, a probable mechanism for electrocatalytic oxidation of cellulose to gluconate in an alkaline condition can be proposed as Scheme 1. As for formate, it displays an inconspicuous increase with the decomposition of gluconate, deduced likely to be the direct oxidation of glucose via α-scission [24,43]. In addition, the total yield of gluconate, oxalate and formate is also calculated and shown in Figure 5.…”

Section: Electrochemical Oxidation Of Cellulosementioning

confidence: 99%

Electrocatalytic Oxidation of Cellulose to Gluconate on Carbon Aerogel Supported Gold Nanoparticles Anode in Alkaline Medium

Xiao

Zhao

2015

Catalysts

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Abstract:The development of high efficient and low energy consumption approaches for the transformation of cellulose is of high significance for a sustainable production of high value-added feedstocks. Herein, electrocatalytic oxidation technique was employed for the selective conversion of cellulose to gluconate in alkaline medium by using concentrated HNO 3 pretreated carbon aerogel (CA) supported Au nanoparticles as anode. Results show that a high gluconate yield of 67.8% and sum salts yield of 88.9% can be obtained after 18 h of electrolysis. The high conversion of cellulose and high selectivity to gluconate could be attributed to the good dissolution of cellulose in NaOH solution which promotes its hydrolysis, the surface oxidized CA support and Au nanoparticles catalyst which possesses high amount of active sites. Moreover, the bubbled air also plays important role in the enhancement of cellulose electrocatalytic conversion efficiency. Lastly, a probable mechanism for electrocatalytic oxidation of cellulose to gluconate in alkaline medium was also proposed.

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Hydrothermal conversion of carbohydrate biomass into formic acid at mild temperatures

Cited by 234 publications

References 19 publications

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Enhanced methane and hydrogen yields from catalytic supercritical water gasification of pine wood sawdust via pre-processing in subcritical water

Electrocatalytic Oxidation of Cellulose to Gluconate on Carbon Aerogel Supported Gold Nanoparticles Anode in Alkaline Medium

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