Simultaneous formation of sorbitol and gluconic acid from cellobiose using carbon-supported ruthenium catalysts

Komanoya, Tasuku; Kobayashi, Hirokazu; Hara, Kenji; Chun, Wang‐Jae; Fukuoka, Atsushi

doi:10.1016/s2095-4956(13)60035-2

Cited by 16 publications

(10 citation statements)

References 12 publications

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“…[27] In Figure 3, the in situ X-ray absorption near-edge structure (XANES) spectra of Ru/AC(N) catalyst recorded at 313-413 K with the heating rate of 10 K min À1 are shown. [34] The distinction owes to the stronger reducing reagent derived from 2-propanol (this study) than that from reducing terminals of sugars (the previous study). In a related work, Davis and co-workers reported the in situ reduction of oxidized Ru species to Ru metal during the hydrogenation of glucose under an H 2 pressure of 4 MPa.…”

Section: Characterization Of Active Ru Species During the Reactionmentioning

confidence: 66%

“…The in situ measurements were performed as follows: cellobiose (205 mg), catalyst (150 mg), and 2propanol/water (0.6:1.8 mL) were charged into a high-pressure PEEK cell (internal volume of 3.5 cm 3 ) covered with a metal frame (SUS 304) having small windows. [34] The reactor was purged with N 2 and then heated to 413 K by two cartridge heaters, and then the quick XAFS spectra were recorded every 0.5 min with a synchrotron radiation (ring energy 6.5 GeV, 50 mA) through a Si(3 3 1) doublecrystal monochromator in the transmission mode. The EXAFS spectra were analyzed by using REX 2000 software (Rigaku) with a spline smoothing method in the range of the wave vector k = 3-15 À1 (k 3 -weighted).…”

Section: Hydrolytic Hydrogenation Of Cellulosementioning

confidence: 99%

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Kinetic Study of Catalytic Conversion of Cellulose to Sugar Alcohols under Low‐Pressure Hydrogen

et al. 2013

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Efficient hydrolytic hydrogenation of cellulose to sugar alcohols under low H2 pressures has remained a challenge. This article deals with the conversion of cellulose by using a carbon‐supported Ru catalyst under H2 pressures as low as 0.7–0.9 MPa (absolute pressure at room temperature). Kinetic studies revealed that the Ru catalyst not only enhances the hydrolysis of cellulose to glucose and hydrogenation of glucose to sugar alcohols (sorbitol and mannitol), but also the degradation of sugar alcohols to C2–C6 polyols and gasses. The degradation path limits the total yield of sugar alcohols to less than 40 %. The yield of sugar alcohols is theoretically improved by increasing the ratio of the reaction rates of the cellulose hydrolysis, which is the rate‐determining step in the reaction, to the decomposition. Thus, a mix‐milling pretreatment of cellulose and the Ru catalyst together selectively accelerated the hydrolysis step and raised the yield up to 68 %, whereas the addition of acids in the cellulose conversion was less effective as a result of promotion of side‐reactions. These results demonstrate superior applicability of the mix‐milling treatment in the depolymerization of cellulose to its monomers.

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Section: Characterization Of Active Ru Species During the Reactionmentioning

confidence: 66%

Section: Hydrolytic Hydrogenation Of Cellulosementioning

confidence: 99%

Kinetic Study of Catalytic Conversion of Cellulose to Sugar Alcohols under Low‐Pressure Hydrogen

et al. 2013

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“…Reduction of glucose to sorbitol via CTH is scarcely reported for catalysts based on Pt, Rh, or Ru [28,29], and only a few contributions focused on using nickel catalysts [29,30]. Thus, Scholz et al [30] studied the CTH of glucose to sorbitol, in the presence of hydrotalcite-derived catalysts (Cu 6−X Ni X Al 2 ), suggesting that Ni-based catalysts, such as Raney-type metal sponges could display notable catalytic activity in the CTH reduction of glucose.…”

Section: Featured Application: Catalytic Transfer Hydrogenation From mentioning

confidence: 99%

“…CTH is, a priori, a more sustainable alternative to conventional hydrogenation with molecular hydrogen because of the lower requirements for high-pressure conditions. CTH is usually performed in the presence of hydrogen donors, such as small alcohols and acids, which can be used under liquid phase conditions and under moderate operation conditions, and which are potentially easily prepared from renewable biomass feedstock [25][26][27].Reduction of glucose to sorbitol via CTH is scarcely reported for catalysts based on Pt, Rh, or Ru [28,29], and only a few contributions focused on using nickel catalysts [29,30]. Thus, Scholz et al [30] studied the CTH of glucose to sorbitol, in the presence of hydrotalcite-derived catalysts (Cu 6−X Ni X Al 2 ), suggesting that Ni-based catalysts, such as Raney-type metal sponges could display notable catalytic activity in the CTH reduction of glucose.…”

mentioning

confidence: 99%

Production of Sorbitol via Catalytic Transfer Hydrogenation of Glucose

et al. 2020

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Featured Application: Catalytic transfer hydrogenation from alcohols allow converting under mild reaction conditions glucose into sorbitol.Abstract: Sorbitol production from glucose was studied through catalytic transfer hydrogenation (CTH) over Raney nickel catalysts in alcohol media, used as solvents and hydrogen donors. It was found that alcohol sugars, sorbitol and mannitol, can be derived from two hydrogen transfer pathways, one produced involving the sacrificing alcohol as a hydrogen donor, and a second one involving glucose disproportionation. Comparison between short-chain alcohols evidenced that ethanol was able to reduce glucose in the presence of Raney nickel under neutral conditions. Side reactions include fructose and mannose production via glucose isomerization, which occur even in the absence of the catalyst. Blank reaction tests allowed evaluating the extension of the isomerization pathway. The influence of several operation parameters, like the temperature or the catalyst loading, as well as the use of metal promoters (Mo and Fe-Cr) over Raney nickel, was examined. This strategy opens new possibilities for the sustainable production of sugar alcohols.Sorbitol production was reported to be carried out using cellulose in the presence of noble metals [9] and transition metal-based catalysts [10,11]. However, a most extended alternative is its production starting from glucose. At an industrial scale, sorbitol is produced via glucose hydrogenation [2] as it is the most affordable precursor [12], whose production is liable to be obtained via cellulose hydrolysis [13,14]. The reaction mechanism consists of the reduction of carbonyl groups of saccharides under hydrogen pressure in the presence of a solid metal catalyst based on Ni, Pd, Pt, or Ru [15,16]. All these catalysts are easily recoverable and display good catalytic activity in terms of sorbitol yield, operating under aqueous-phase solution [6,[17][18][19][20]. In recent years, Raney nickel and ruthenium catalysts made a clean sweep on sorbitol production. Ru presents higher activity and selectivity to sorbitol [16,21] than Raney nickel catalysts, but this metal is much more expensive than nickel-based catalysts. In this way, Raney nickel was revealed as the most interesting active phase to be used in the industrial-scale hydrogenation of glucose [21,22], mostly because of its low price [23]. Nevertheless, the lower catalytic activity of nickel as compared to other precious-metal-based conventional hydrogenation catalysts, such as ruthenium, results in the need for high hydrogen pressure and harsh operating conditions. Consequently, a significant energy demand must be satisfied compared to that required when using more active hydrogenation catalysts and, thus, higher environmental impacts are associated with the use of Raney nickel catalysts [24].This work focuses on gaining insights into a developing alternative reaction pathway to the conventional hydrogenation procedure used to transform glucose into sorbitol by exploring the feasibility of car...

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“…Catalytic depolymerisation of cellulose is aimed at the selective production of glucose. Glucose can be eventually further upgraded via consecutive catalytic processes such as oxidation, hydrogenation or dehydration to form platform chemicals or biofuels, applying the strategy of cascade reactions in one‐pot . However, the large incompatibility between much higher feedstock stability (i. e. cellulose or cellobiose) when compared to that of the product (i. e. glucose), is the reason for the continuous search for novel catalytic technologies that can operate under milder reaction conditions .…”

Section: Introductionmentioning

confidence: 99%

Cutting the Green Waste. Structure‐Performance Relationship in Functionalized Carbon Xerogels for Hydrolysis of Cellobiose

et al. 2018

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The hydrolysis of cellulose and hemicelluloses in the presence of solid acid catalysts is of great importance as an entry process for the production of biofuels and chemicals. In this work, the effect of carbon surface chemistry on the catalyst conversion and selectivity in hydrolysis of cellobiose to glucose was studied. Solid catalysts based on carbon xerogels (CXs) containing various functionalities incorporating heteroatoms (S, P, N, O), as confirmed by XPS, TPD, ICP and EA analyses, were successfully prepared. CXs containing 3.4 wt % of phosphorus showed the best catalytic performance, reaching 90 % con-version of cellobiose with 72 % selectivity to glucose, under oxidative atmosphere and in a short reaction time of only 4 h. The presence of phosphonates (ÀPÀCÀ) was found to increase the selectivity to glucose up to unprecedented 87 %. On the contrary, carbonyls, quinones, pyrydinic, pyrrolic and sulfonic groups were found to promote glucose degradation, leading to a final low yield of this product. Additionally, the increased concentration of oxygen in the reaction atmosphere was shown to significantly weaken the b (1-4)-glycosidic bond, increasing the final yield of glucose.[a] Dr.

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Simultaneous formation of sorbitol and gluconic acid from cellobiose using carbon-supported ruthenium catalysts

Cited by 16 publications

References 12 publications

Kinetic Study of Catalytic Conversion of Cellulose to Sugar Alcohols under Low‐Pressure Hydrogen

Kinetic Study of Catalytic Conversion of Cellulose to Sugar Alcohols under Low‐Pressure Hydrogen

Production of Sorbitol via Catalytic Transfer Hydrogenation of Glucose

Cutting the Green Waste. Structure‐Performance Relationship in Functionalized Carbon Xerogels for Hydrolysis of Cellobiose

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