Yield Of Sorbitol Research Articles

Corn stover-derived biochar supporting dual functional catalyst for direct sorbitol production from cellulosic materials

Sorbitol is one of the top twelve platform chemicals and is industrially produced via glucose hydrogenation reaction. Direct sorbitol production from cellulosic material using a low-cost catalyst is a current challenge. In this study, corn stover-derived biochar supporting dual functional catalyst (Ru/S-CCS) was prepared and extensively characterized. The Ru/S-CCS catalyst was used for direct sorbitol production from microcrystalline cellulose at various reaction temperatures (180–220 °C), times (3–18 h), H2 pressures (1–5 MPa), and Ru contents (1–5 %). The maximum sorbitol yield (66.3 wt%) and selectivity (66.1 %) were achieved at 220 °C for 6 h under 5 MPa H2 with 5 % Ru. Various catalyst characterization techniques revealed that the acidic characteristics and metal hydrogenation sites of the Ru/S-CCS played a vital role in direct sorbitol production from cellulose. The sorbitol yield and selectivity could be enhanced by the vigorous interactive effect of sulfonic groups and Ru metal sites. The recycling performance of the Ru/S-CCS catalyst was explored under the optimal reaction conditions. Moreover, sorbitol production from glucose, raw CS, and pretreated CS was further investigated. Overall, the results of this study show that the CS biochar used in Ru/S-CCS preparation can be a competitive material for the catalyst preparation in sorbitol production, which may subsequently be used for designing large-scale sugar alcohol production.

Producing sorbitol from cellulose over Ru-WOX co-doped biochars catalysts

In this work, bifunctional Ru-WOX support on four kinds of biochars using as hydrogenation catalysts to convert cellulose into sorbitol. Four biochar including walnut shell (WS), eucalyptus lignin (EL), pine lignin (PN), and corn cob (CN). The Ru-WOX/biochar catalysts were characterized, and the performance of the catalysts were studied under various conditions. It showed that biochar supports have significantly affected on hydrogenation activity, the sorbitol yields have the order of WS > PN > EL > CN, and found that Ru-WOX/WS achieved 100% cellulose conversion and sorbitol yield as high as 82.6% at 220°C for 4 h, and 3 MPa H2 pressure. The relation of structure-performance showed that biochar from WS facilitated the formation of Ru0 due to its larger specific surface area as well as high ratio of Ru0/Ru4+. The catalytic performance has not changed after using 5 times.

Hydrogenation of glucose to sorbitol by using nickel hydroxyapatite catalyst

AbstractA series of nickel hydroxyapatite catalysts were synthesized by the co‐precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni‐HAP catalyst with comparatively high surface area and acid‐base strength gave high sorbitol selectivity in 1 h. Ni‐HAP‐4 catalyst with moderate Ni (3.5 wt. %) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97 % in 1 h. The Ni‐HAP‐4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM‐EDS, BET, NH3‐TPD, and CO2‐TPD were employed to analyze the Ni‐HAP‐4 catalyst.

Green and efficient utilization of beech sawdust waste for sorbitol production: Direct conversion residue via Ru2P/OMC derived from separated lignin

This paper proposes a green and sustainable strategy to achieve efficient utilization of beech sawdust waste to produce sorbitol. First, ethanol dissolution method was used to extract lignin from sawdust. Subsequently, the lignin combined with phloroglucinol were used to fabricate ordered mesoporous carbon (OMC) using solvent evaporation induced self-assembly (EISA) method. Afterwards, Ru2P/OMC was synthesized and utilized as a catalyst for the production of sorbitol from the residue using pure water as green solvent. Finally, the yield of sorbitol and xylitol reached 77.2 % and 12.5 % at 200 °C in 5 h, respectively. Different characterization techniques were used to reveal the structural composition of the catalysts and the mechanism of the reaction. The results show that the bifunctional Ru2P/OMC catalyst has dual activity of hydrolysis and hydrogenation without sulfonation treatments. Interestingly, the bifunctional Ru2P/OMC catalyst has satisfactory activity, selectivity, and stability, which is promising in biomass waste conversion.

Production of Sorbitol via Hydrogenation of Glucose over Ruthenium Coordinated with Amino Styrene-co-maleic Anhydride Polymer Encapsulated on Activated Carbon (Ru/ASMA@AC) Catalyst.

Sorbitol, a product primarily derived from glucose hydrogenation, has extensive applications in the pharmaceutical, chemical and other industries. Amino styrene-co-maleic anhydride polymer encapsulated on activated carbon (Ru/ASMA@AC) catalysts were developed for efficient glucose hydrogenation and were prepared and confined Ru by coordination with styrene-co-maleic anhydride polymer (ASMA). Through single-factor experiments, optimal conditions were determined to be 2.5 wt.% ruthenium loading and a catalyst usage of 1.5 g, 20% glucose solution at 130 °C, reaction pressure of 4.0 MPa, and a stirring speed of 600 rpm for 3 h. These conditions achieved a high glucose conversion rate of 99.68% and a sorbitol selectivity of 93.04%. Reaction kinetics testing proved that the hydrogenation of glucose catalyzed by Ru/ASMA@AC was a first-order reaction, with a reaction activation energy of 73.04 kJ/mol. Furthermore, the catalytic performance of the Ru/ASMA@AC and Ru/AC catalysts for glucose hydrogenation were compared and characterized by various detection methods. The Ru/ASMA@AC catalyst exhibited excellent stability after five cycles, whereas the traditional Ru/AC catalyst suffered from a 10% decrease in sorbitol yield after three cycles. These results suggest that the Ru/ASMA@AC catalyst is a more promising candidate for high-concentration glucose hydrogenation due to its high catalytic performance and superior stability.

Biomass derived bifunctional catalyst for the conversion of cassava dreg into sorbitol

A biomass derived bifunctional catalyst (Ru/CCD-SO3H) was used for one-pot conversion of cassava dreg and cassava starch into sorbitol. The cassava dreg is mainly composed of residual cassava starch and holocellulose. The highest sorbitol yield of 11.43 % was achieved using cassava dreg as reactant. A synergistic catalytic effect of acid and metal sites of Ru/CCD-SO3H on cassava starch conversion to sorbitol was observed. The maximum sorbitol yield reached 82.51 % using cassava starch as reactant. A kinetic model of cassava starch degradation was performed. The reaction rate constants of cassava starch degradation, glucose conversion and sorbitol generation improved with enhancing temperature. The activation energy of cassava starch hydrolysis is larger than that of glucose hydrogenation, indicating the cassava starch hydrolysis is rate-determining step of cassava starch conversion into sorbitol. This work not only realizes the comprehensive utilization of cassava dreg, but also provides useful guidance for developing kinetic model of polysaccharide conversion.

Optimisation of the processing conditions of hydrolytic hydrogenation of cellulose using carbon nanofiber supported Ni catalysts

The synthesis of sorbitol from cellulose over Ni catalysts is a promising valorisation route in the biorefinery scenario, applying relatively simple preparation methods and earth-abundant metals. The overall selectivity, however, depends on the kinetic control of a complex reaction network, involving the hydrolysis of cellulose to monosaccharides via cello-oligomers, glucose hydrogenation into sorbitol and hydrogenolysis side-reactions of sugars and sorbitol to low molecular weight polyols. Therein, subtle changes in the catalyst composition and process conditions might have a strong impact on the final product distribution. Driven by these challenges, this work first-time provides novel insights into the hydrothermal hydrogenation of cellulose over a carbon nanofibre supported Ni catalyst (Ni/CNF). Firstly, the impact of the duration of a ball-milling pre-treatment step and the influences of the hydrothermal time and temperature were thoroughly analysed. The experimental results obtained highlighted the importance of process control to promote the first transformation of cellulose to glucose and its subsequent hydrogenation to sorbitol to minimise the extension of side reactions. Finally, an additional study was conducted to palliate the recalcitrant nature of cellulose by decreasing mass transfer limitations to a minimum extent. This was achieved by including an additional mix-milling of the amorphous cellulose produced in the first pre-treatment with the catalyst and increasing the H2 pressure of the hydrothermal hydrogenation process. This allowed attaining a sorbitol yield as high as 62% at 190 ºC using an initial H2 pressure of 8 MPa for 26 h, which is one of the best results reported in the literature.

Role of Calcination Temperature on Isosorbide Production from Sorbitol Dehydration over the Catalyst Derived from Ce(IV) Sulfate

Isosorbide is a multi-purpose chemical that can be produced from renewable resources. Specifically, it has been investigated as a replacement for toxic bisphenol A (BPA) in the production of polycarbonate (PC). In this study, the synthesis of isosorbide by sorbitol dehydration using a cerium-based catalyst derived from calcined cerium (IV) sulfate (300°C, 400°C, 450°C, 500°C, and 650°C) was investigated. The reaction occurred in a high-pressure reactor containing nitrogen gas. Advanced instrumental techniques were applied to analyze the characteristics of the calcined catalyst. The results showed that the calcined catalysts demonstrated different crystalline structures and sulfate species at different temperatures. However, the acidic properties (strength and amount) of the catalyst did not change with the calcination temperature. The cerium (IV) sulfate calcined at 400°C exhibited the best catalytic performance, achieving the highest isosorbide yield (55.7%) and complete conversion of sorbitol at 180°C, 20 bar of N2, and 6 h using CeSO-400. The presence of a sulfate group on the catalyst was the most important factor in determining the catalytic performance of sorbitol dehydration to isosorbide. This work suggests that CeSO-400 catalysts may play an important role in reducing reaction conditions.

Directly converting cellulose into high yield sorbitol by tuning the electron structure of Ru2P anchored in agricultural straw biochar

Directly converting cellulose into sorbitol involves efficient synergy of cellulose hydrolysis and glucose hydrogenation in a bifunctional catalyst. High temperature is favorable and efficient for cellulose hydrolysis, but easily causes the excessive hydrogenation of sorbitol. In this paper, we propose a new strategy to appropriately regulate the hydrogenation activity of Ru catalysts by partially shifting the electrons from Ru to P, which could reduce excessive hydrogenation of sorbitol at 180–200 °C and thus enhance the sorbitol yield. The rice straw biochar was used as carrier and Ru2P/C was synthesized for obtaining sorbitol from glucose by hydrogenation. Subsequently, the bifunctional catalyst Ru2P/C–SO3H was prepared for directly converting cellulose into sorbitol, and the relationship between the composition of the as-prepared catalyst and the sorbitol yield was systematically studied. Satisfactorily, 2 wt% Ru2P/C–SO3H gave sorbitol yields of 96% and 64% at 200 °C within 2 h when glucose and cellulose were used as raw materials, respectively. The characterization results and DFT calculations show that the electrons of Ru atoms in Ru2P are partially transferred to P, which weakens the adsorption and activation of H2 and H* on Ru atoms, thus improving the selectivity of sorbitol. Moreover, Ru2P/C–SO3H has a potential ability in natural biomass waste utilization.

One‐pot Catalytic Conversion of Cellulose to Sorbitol and Isosorbide over Bifunctional Ni/TaOPO4 Catalysts

AbstractPreparation of isosorbide from cellulose by a catalytic one‐pot method under hydrothermal conditions is studied. Phosphate tantalum (TaOPO4) was prepared and used as support for the preparation of Ni/TaOPO4 via impregnation of Ni. The catalyst was characterized by X‐ray diffraction, H2‐TPR, NH3‐TPD, pyridine FTIR and Raman spectroscopy analysis. Results showed that the 5Ni/TaOPO4 (5 % loading of Ni) with a Brønsted/Lewis site (B/L) ratio of 0.153 showed the best catalytic performance and the total yields of sorbitol and isosorbide from cellulose reached 43 % under the conditions of 200 °C and 3 MPa H2 for 24 h. Both Lewis and Brønsted acid sites played crucial roles for the decomposition and dehydration reactions. The synergy of surface acid sites and reduction sites enhanced the cascade dehydration and hydrogenation reactions during the conversion of cellulose to isosorbide. This research is expected to broach a solution for the development of novel solid acid catalysts for the conversion of sugars into platform compounds.

Selective hydrogenation of glucose to sorbitol with tannic acid-based porous carbon sphere supported Ni–Ru bimetallic catalysts

Ni–Ru bimetallic porous carbon sphere (Ni–Ru@PCS) catalysts were synthesized via formaldehyde-assisted, metal-coordinated crosslinking sol–gel chemistry, in which biomass-derived tannic acid and F127 surfactant were used as carbon precursor and soft template, respectively, and Ni2+ and Ru3+ were used as cross-linkers. In the developed method, Ni–Ru particles became uniformly dispersed in the carbon skeleton due to strong coordination bonds between metal ions (Ni2+ and Ru3+) and tannic acid molecules and bimetal interactions. The as-synthesized Ni–Ru10:1@PCS catalyst with a loading Ni:Ru mole ratio of 10:1 was applied for the selective hydrogenation of glucose to sorbitol, and provided 99% glucose conversion with a sorbitol selectivity of 100% at 140 °C in 150 min reaction time and exhibited good stability and recyclability in which sorbitol yield remained at 98% after 4 cycles with little or no metal agglomeration. The catalyst was applied to glucose solutions as high as 20 wt% with 97% sorbitol yields being obtained at 140 °C in 20 h. The developed bimetallic porous carbon sphere catalysts take advantage of sustainably-derived materials in their structure and are applicable to related biomass conversion reactions.

Selective catalytic hydrogenation of cellulose into sorbitol with Ru-based catalysts

Sorbitol is one of the platform chemicals and can be produced from various renewable and sustainable sources via different processes. Hydrothermal liquefaction is an effective and promising approach to produce sorbitol, since the subcritical reaction media and appropriate catalysts provide a selective production of platform chemicals. In this study, sorbitol was produced from different renewable sources (cellulose and glucose) in the presence of Ru-based catalysts (Ru/SiO2, Ru/AC, Ru/SBA-15, and Ru/SBA-15-SO3) under subcritical conditions. The highest cellulose conversion was achieved as 90% in the presence of Ru/SBA-15-SO3 for 1 h of reaction duration. The highest sorbitol yield (%) by hydrothermal liquefaction of cellulose was obtained as 6.2% by using Ru/AC for 1 h of reaction duration. A total of 99.9% of glucose conversion was achieved in the presence of all catalysts. The highest sorbitol yield (%) by hydrothermal liquefaction of glucose was found as 3.8% for 1 h of reaction duration. Owing to the results of GC-MS analysis, the intermediate products were identified, and, thus, a reaction pathway was proposed.

Enzymatic depolymerization of wheat straw polysaccharides

The purpose of this study is to develop a technology for enzymatic processing for depolymerization of polysaccharides in wheat straw to obtain the maximum yield of glucose and sorbitol. Cellulolytic enzymes endo-1,4-β-glucanase (EC 3.2.1.4) and cellobiose (1,3-β-glucosidase) (CF 3.2.1.21) were isolated and studied in local strains Tr. viride 121, which are grown under deep cultivation conditions. A technology has been developed for obtaining a complex preparation “Cellozyme G20x” with a high yield and specific activity of cellulase, xylanase, β-glucanase and pectinase, and a scheme for purification from cellulases by precipitation, ultrafiltration, and freeze drying is not inferior in efficiency to commercial preparations. The physicochemical properties of the preparation “Cellozyme G20x” have been studied, the optimal parameters of the action and stability of the enzyme preparation have been established. The efficiency of Cellozyme G20x for hydrolysis of straw polysaccharides was 35-40% in terms of glucose yield.

Hydrolytic Hydrogenation of Cellulose with the Use of the Ru-containing Polymeric Catalysts

The study presents the results of cellulose hydrolytic hydrogenation process in subcritical water in the presence of Ru-containing catalysts based on hypercrosslinked polystyrene (HPS) MN-270 and its functionalized analogues: NH2-HPS (MN-100) and SO3H-HPS (MN-500). It was shown that the replacement of the traditional support (carbon) by HPS increases the yield of the main cellulose conversion products – polyols – important intermediates for the chemical industry. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0% Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50% on the average at 85% cellulose conversion.

Selective catalytic hydrogenation of cellulose into sorbitol with Ru-based catalysts.

Sorbitol is one of the platform chemicals and can be produced from various renewable and sustainable sources via different processes. Hydrothermal liquefaction is an effective and promising approach to produce sorbitol, since the subcritical reaction media and appropriate catalysts provide a selective production of platform chemicals. In this study, sorbitol was produced from different renewable sources (cellulose and glucose) in the presence of Ru-based catalysts (Ru/SiO2, Ru/AC, Ru/SBA-15, and Ru/SBA-15-SO3) under subcritical conditions. The highest cellulose conversion was achieved as 90% in the presence of Ru/SBA-15-SO3 for 1 h of reaction duration. The highest sorbitol yield (%) by hydrothermal liquefaction of cellulose was obtained as 6.2% by using Ru/AC for 1 h of reaction duration. A total of 99.9% of glucose conversion was achieved in the presence of all catalysts. The highest sorbitol yield (%) by hydrothermal liquefaction of glucose was found as 3.8% for 1 h of reaction duration. Owing to the results of GC-MS analysis, the intermediate products were identified, and, thus, a reaction pathway was proposed.

Efficient Sorbitol Producing Process through Glucose Hydrogenation Catalyzed by Ru Supported Amino Poly (Styrene-co-Maleic) Polymer (ASMA) Encapsulated on γ-Al2O3

In this work, a core-shell-like sphere ruthenium catalyst, named as 5%Ru/γ-Al2O3@ASMA, has been successfully synthesized through impregnating the ruthenium nanoparticles (NPs) on the surface of the amino poly (styrene-co-maleic) polymer (ASMA) encapsulating γ-Al2O3 pellet support. The interaction between the Ru cations and the electro-donating polymer shell rich in hydroxyl and amino groups through the coordination bond would guarantee that the Ru NPs can be highly dispersed and firmly embedded on the surface of the support. In addition, the solid sphere γ-Al2O3 pellet could serve as the core to support the resulted catalysts applied in the flow process in a trickle bed reactor to promote the productivity. The resulted catalyst 5%Ru/γ-Al2O3@ASMA can be applied efficiently in the glucose hydrogenation and presents a steadfast sorbitol yield of almost 90% both in batch reactor and the trickle bed reactor, indicating the potential feasibility of the core-shell-like catalyst in the efficient production of sorbitol.

One-pot synthesis of sorbitol via hydrolysis-hydrogenation of cellulose in the presence of Ru-containing composites

The aim of this work was to study the one-pot synthesis of sorbitol via hydrolysis-hydrogenation of cellulose in the presence of Ru-containing composites based on H3PW12O40 supported on ZrO2 and Nb2O5 (Ru-PW/ZrO2 and Ru-PW/Nb2O5). The main parameters impacted the reaction rate and yield of sorbitol, i.e. reaction conditions and type of catalyst were investigated. Ru-PW/ZrO2 systems were more active than Ru-PW/Nb2O5. The yield of sorbitol was found to depend on the activation temperature of PW/ZrO2 and PW/Nb2O5 which affected textural properties, the amount of acid sites and size of Ru nanoparticles. The highest 66% sorbitol yield was observed in the presence of 3%Ru-PW/ZrO2 activated at 550 °C and 1/1 of weight ratio of cellulose/catalyst, 180 °C, 7 MPa hydrogen pressure. This catalyst was stable for three cycles of the reaction without lost of it's activity.

A Robust and Highly Selective Catalytic System of Copper-Silica Nanocomposite and 1-Butanol in Fructose Hydrogenation to Mannitol.

We report for the first time the selective production of mannitol, a low-calorie sweetener and an important pharmaceutical ingredient, from fructose using Cu-SiO2 nanocomposite as catalyst and 1-butanol as solvent. When compared with water and ethanol, a lower fructose solubility was achieved in 1-butanol, which caused a lower fructose conversion and higher mannitol selectivity by reducing formation of side products. Among various Cu-based catalysts in 1-butanol, Cu(80)-SiO2 nanocomposite gave an unprecedented mannitol (83 %) and sorbitol (15 %) yield at 120 °C, 35 bar H2 , and 10 h reaction time. More importantly, this catalyst did not show any Cu leaching and its physicochemical properties were maintained after liquid-phase fructose hydrogenation whereas other Cu-based catalysts such as Cu(32)-Cr2 O and Cu(66)-ZnO did show significant leaching of Cu and Cr. Thus, Cu(80)-SiO2 nanocomposite and 1-butanol are regarded as a robust and highly efficient catalytic system for the selective hydrogenation of fructose to mannitol. Also, density functional theory calculations supported that in addition to the stable initial structure of adsorbed fructose, the mannitol pathway was more thermodynamically favorable than the sorbitol pathway. Notably, the highly pure mannitol (99 %) could be recovered from the sorbitol-containing 1-butanol solution by simple filtration. Therefore, the present protocol is a novel and effective method to produce pure mannitol from fructose in both an environmental and an industrial context.

The main factors affecting the catalytic properties of Ru/Cs-HPA systems in one-pot hydrolysis-hydrogenation of cellulose to sorbitol

One-pot conversion of mechanically activated cellulose to sorbitol was investigated over bifunctional catalysts based on Ru (0.6, 1 and 3 wt.%) and cesium salts of heteropoly acids (HPA) Cs2.1H0.9PW12O40 and Cs3HSiW12O40 (Cs-PW and Cs-SiW, respectively). The maximal yield of sorbitol equal to 59 % and selectivity 94 % were achieved over the 1%Ru/Cs3HSiW12O40 catalyst. Physicochemical and catalytic data showed that the rate-determining step, i.e. the hydrolysis of cellulose, depended on the surface acidity of catalysts, whereas Ru content in catalyst affected both the hydrolysis and the hydrogenation steps. The kinetic parameters for one-pot conversion of cellulose were determined by mathematical modeling approach and were successfully used for the prediction of the yields of sorbitol and mannitol.

Effective Conversion of Cellulose to Sorbitol Catalyzed by Mesoporous Carbon Supported Ruthenium Combined with Zirconium Phosphate

The selective conversion of cellulose to sorbitol is a promising route to valorize biomass. A binary catalyst ZrP-Ru/MC was constructed by mesoporous carbon supported ruthenium (Ru/MC) combined with zirconium phosphate (ZrP). It was found that ZrP-Ru/MC was an excellent catalyst for the conversion of cellulose with high sorbitol yield. Under the optimal reaction condition, a high sorbitol yield of 66.4% was obtained in just 1.5 h if cellulose was mix-milled together with ZrP. The characterizations results indicated that the high dispersion of Ru and macroporous–mesoporous structure were the key factor to determine the excellent catalytic activity of Ru/MC. In addition, the Ru TOF of 220 h−1 in the Ru/MC was much higher than that of commercial ruthenium carbon, indicating the high Ru utilization in Ru/MC.