Efficient Hydrogenation of Xylose and Hemicellulosic Hydrolysate to Xylitol over Ni-Re Bimetallic Nanoparticle Catalyst.
ABSTRACT: A disadvantage of the commercial Raney Ni is that the Ni active sites are prone to leaching and deactivation in the hydrogenation of xylose to xylitol. To explore a more stable and robust catalyst, activated carbon (AC) supported Ni-Re bimetallic catalysts (Ni-Re/AC) were synthesized and used to hydrogenate xylose and hemicellulosic hydrolysate into xylitol under mild reaction conditions. In contrast to the monometallic Ni/AC catalyst, bimetallic Ni-Re/AC exhibited better catalytic performances in the hydrogenation of xylose to xylitol. A high xylitol yield up to 98% was achieved over Ni-Re/AC (nNi:nRe = 1:1) at 140 °C for 1 h. In addition, these bimetallic catalysts also had superior hydrogenation performance in the conversion of the hydrolysate derived from the hydrolysis reaction of the hemicellulose of Camellia oleifera shell. The characterization results showed that the addition of Re led to the formation of Ni-Re alloy and improved the dispersion of Ni active sites. The recycled experimental results revealed that the monometallic Ni and the bimetallic Ni-Re catalysts tended to deactivate, but the introduction of Re was able to remarkably improve the catalyst's stability and reduce the Ni leaching during the hydrogenation reaction.
Project description:Carbon-supported mono- and bimetallic catalysts prepared via incipient wetness impregnation were systematically studied in aqueous-phase reforming (APR) of xylitol aiming at hydrogen production from biomass. The catalytic performance of several VIII group metals and their combinations, such as Pt, Ni, Pt-Ni, Re, Pt-Re, Ru, Pt-Ru, and Pt-Co, was compared for xylitol APR in a fixed-bed reactor at 225 °C and 29.7 bar (N2). Ni/C, Ru/C, and Re/C catalysts displayed significantly lower activity compared to others. Activity and selectivity to H2 of bimetallic Pt-Ni/C, Pt-Co/C, and Pt-Ru/C catalysts were close to that of Pt/C. Pt-Re/C catalyst showed an outstanding performance which was accompanied by a shift of the reaction pathways to the alkane formation and thereby lower hydrogen selectivity. Addition of the second metal to Pt was not found to be beneficial for hydrogen production, thus leaving Pt/C as the optimum carbon-supported catalyst.
Project description:The catalytic hydrogenation of lactic acid to 1,2-propanediol with supported Ru catalysts in water was investigated. The influence of catalyst support (activated carbon, ?-Al2O3, SiO2, TiO2, and CeO2) and promoters (Pd, Au, Mo, Re, Sn) on the catalytic performance was evaluated. Catalytic tests revealed that TiO2 yields the best Ru catalysts. With a monometallic Ru/TiO2 catalyst, a 1,2-propanediol yield of 70?% at 79?% lactic acid conversion was achieved at 130?°C after 20?h reaction. Minor byproducts of the hydrogenation reaction were propionic acid, ethanol, 1-propanol, and 2-propanol. For the bimetallic catalysts, the addition of Pd and Au slightly enhanced the performance of Ru/TiO2, whereas the addition of common hydrogenation promoters such as Re, Mo, and Sn impaired the activity.
Project description:Ethylene is an important chemical raw material and with the increasing consumption of petroleum resources, the production of ethylene through the calcium carbide acetylene route has important research significance. In this work, a series of bimetallic catalysts with different Cu/Ni molar ratios are prepared by co-impregnation method for the hydrogenation of calcium carbide acetylene to ethylene. The introduction of an appropriate amount of Cu effectively inhibits not only the formation of ethane and green oil, thus increasing the selectivity of ethylene, but also the formation of carbon deposits, which improves the stability of the catalyst. The ethylene selectivity of the Ni-Cu bimetallic catalyst increases from 45% to 63% compared with the Ni monometallic counterpart and the acetylene conversion still can reach 100% at the optimal conditions of 250 °C, 8000 mL·g-1·h-1 and V(H2)/V(C2H2) = 3. X-ray diffraction and transmission electron microscopy confirmed that the metal particles were highly dispersed on the support, High-resolution transmission electron microscopy and H2-Temperature programmed reduction proved that there was an interaction between Ni and Cu, combined with X-ray photoelectron spectroscopy and density functional theory calculations results, Cu transferred electrons to Ni changed the Ni electron cloud density in NiCux catalysts, thus reducing the adsorption of acetylene and ethylene, which is favorable to ethylene selectivity.
Project description:Xylitol is one of the most famous chemicals known to people as the essential ingredient of chewing gum and as the sugar alternative for diabetics. Catalytic hydrogenation of biomass-derived xylose with H2 to produce high-value xylitol has been carried out under harsh reaction conditions. Herein, we exhibit the combination of Ru NPs with an environmentally benign MOF (ZIF-67) to afford a heterogeneous composite catalyst. Complete conversion of xylose with 100% selectivity to xylitol was achieved at 50°C and 1?atm H2. This is the first successful attempt to produce xylitol with ambient pressure H2 as well as the first time to achieve a 100% selectivity of xylitol for applicable catalysts. We also proved the universality of the Ru@ZIF-67 towards other hydrogenation processes. Under 1?atm H2, we achieved 100% conversion and >99% selectivity of 1-phenylethanol at 50°C for the hydrogenation of acetophenone. This is also the first report of hydrogenating acetophenone to 1-phenylethanol under 1?atm H2, which confirms that our result not only contributes to enhance the industrial yields of xylitol and reduces both the economical and energy costs but also provides new perspectives on the other hydrogenation process with H2.
Project description:Xylitol is a sugar alcohol with five carbons that can be used in the pharmaceutical and food industries. It is industrially produced by chemical route; however, a more economical and environmentally friendly production process is of interest. In this context, this study aimed to select wild yeasts able to produce xylitol and compare their performance in sugarcane bagasse hydrolysate. For this, 960 yeast strains, isolated from soil, wood, and insects have been prospected and selected for the ability to grow on defined medium containing xylose as the sole carbon source. A total of 42 yeasts was selected and their profile of sugar consumption and metabolite production were analyzed in microscale fermentation. The six best xylose-consuming strains were molecularly identified as Meyerozyma spp. The fermentative kinetics comparisons on defined medium and on sugarcane bagasse hydrolysate showed physiological differences among these strains. Production yields vary from YP/S = 0.25 g/g to YP/S = 0.34 g/g in defined medium and from YP/S = 0.41 g/g to YP/S = 0.60 g/g in the hydrolysate. Then, the xylitol production performance of the best xylose-consuming strain obtained in the screening, which was named M. guilliermondii B12, was compared with the previously reported xylitol producing yeasts M. guilliermondii A3, Spathaspora sp. JA1, and Wickerhamomyces anomalus 740 in sugarcane bagasse hydrolysate under oxygen-limited conditions. All the yeasts were able to metabolize xylose, but W. anomalus 740 showed the highest xylitol production yield, reaching a maximum of 0.83 g xylitol/g of xylose in hydrolysate. The screening strategy allowed identification of a new M. guilliermondii strain that efficiently grows in xylose even in hydrolysate with a high content of acetic acid (~6 g/L). In addition, this study reports, for the first time, a high-efficient xylitol producing strain of W. anomalus, which achieved, to the best of our knowledge, one of the highest xylitol production yields in hydrolysate reported in the literature.
Project description:Designing nanocatalysts with synergetic functional component is a desirable strategy to achieve both high activity and selectivity for industrially important hydrogenation reaction. Herein, we fabricated a core-shell hollow Au@Pt NTs@ZIFs (ZIF, zeolitic imidazolate framework; NT, nanotube) nanocomposite as highly efficient catalysts for semi-hydrogenation of acetylene. Hollow Au@Pt NTs were synthesized by epitaxial growth of Pt shell on Au nanorods followed with oxidative etching of Au@Pt nanorod. The obtained hollow Au@Pt NTs were then homogeneously encapsulated within ZIFs through in situ crystallization. By combining the high activity of bimetallic nanotube and gas enrichment property of porous metal-organic frameworks, hollow Au@Pt NT@ZIF catalyst was demonstrated to show superior catalytic performance for the semi-hydrogenation of acetylene, in terms of both selectivity and activity, over those of monometallic Au and solid bimetal nanorod@ZIF counterparts. This catalysts design idea is believed to be inspirable for the development of highly efficient nanocomposite catalysts.
Project description:A ceria (CeO2) promoted Cu-Ni bimetallic catalyst supported on SiO2 (Cu-Ni/CeO2-SiO2) was prepared and evaluated for catalytic hydrodeoxygenation (HDO) of vanillin. Silica supported monometallic Cu and Ni catalysts and bimetallic Cu-Ni catalyst (Cu/SiO2, Ni/SiO2, and Cu-Ni/SiO2), without a ceria promoter, were also synthesized and tested for the same application. The highest conversion of vanillin was achieved with the Cu-Ni/CeO2-SiO2 catalyst. Vanillyl alcohol was the sole product in the initial 2 h, followed by the formation of 2-methoxy-4-methylphenol, which was observed. Characterization of the synthesized catalysts revealed the presence of overlapping crystalline phases of CuO, NiO, and CeO2 on the Cu-Ni/CeO2-SiO2 surface. We extended our study to find out the results of using CeO2 as the support of the Cu-Ni bimetallic catalyst (Cu-Ni/CeO2). Partial incorporation of Cu and Ni cations into the ceria lattice took place, leading to the decrease of specific surface area and a concomitant compromise in the conversion. In the case of the Cu-Ni/CeO2-SiO2 catalyst, the higher conversion was accredited to the facile formation of Cu+ active centers by the synergistic interaction between Ce+4/Ce+3 and Cu+2/Cu+ redox couples and the incorporation of oxygen vacancies on the catalyst surface.
Project description:Xylitol production was compared in fed batch fermentation by Saccharomyces cerevisiae strains overexpressing xylose reductase (XR) genes from Candida tropicalis, Pichia stipitis, Neurospora crassa, and an endogenous gene GRE3. The gene encoding a xylose specific transporter (SUT1) from P. stipitis was cloned to improve xylose transport and fed batch fermentation was used with glucose as a cosubstrate to regenerate NADPH. Xylitol yield was near theoretical for all the strains in fed batch fermentation. The highest volumetric (0.28 gL-1 h-1) and specific (34 mgg-1 h-1) xylitol productivities were obtained by the strain overexpressing GRE3 gene, while the control strain showed 7.2 mgg-1 h-1 specific productivity. The recombinant strains carrying XR from C. tropicalis, P. stipitis, and N. crassa produced xylitol with lower specific productivity of 14.3, 6.8, and 6.3 mgg-1 h-1, respectively, than GRE3 overexpressing strain. The glucose fed as cosubstrate was converted to biomass and ethanol, while xylose was only converted to xylitol. The efficiency of ethanol production was in the range of 38-45 % of the theoretical maximum for all the strains. Xylitol production from the non-detoxified corncob hemicellulosic hydrolysate by recombinant S. cerevisiae was reported for the first time. Xylitol productivity was found to be equivalent in the synthetic xylose as well as hemicellulosic hydrolysate-based media showing no inhibition on the S. cerevisiae due to the inhibitors present in the hydrolysate. A systematic evaluation of heterologous XRs and endogenous GRE3 genes was performed, and the strain overexpressing the endogenous GRE3 gene showed the best xylitol productivity.
Project description:The impregnation method is commonly employed to prepare supported multi-metallic catalysts but it is often difficult to achieve homogeneous and stable alloy structures. In this work, we revealed the dependence of alloying behavior on the support morphology by fabricating Ni-Cu over different shaped CeO2. Specifically, nanocube ceria favoured the formation of monometallic Cu and Ni-rich phases whereas polycrystalline and nanorod ceria induced the formation of a mixture of Cu-rich alloys with monometallic Ni. Surprisingly, nanopolyhedron (NP) ceria led to the generation of homogeneous Ni-Cu nanoalloys owing to the equivalent interactions of Ni and Cu species with CeO2 (111) facets which exposed relatively few coordinative unsaturated sites. More importantly, a strong interfacial effect was observed for Ni-Cu/CeO2-NP due to the presence of CeO x adjacent to metal sites at the interface, resulting in excellent stability of the alloy structure. With the aid of CeO x , NiCu nanoalloys showed outstanding catalytic behaviour in acetylene and hexyne hydrogenation reactions. This study provides valuable insights into how fully alloyed and stable catalysts may be prepared by tailoring the support morphology while still employing a universal impregnation method.
Project description:Fermentation of the pentose sugar xylose to ethanol in lignocellulosic biomass would make bioethanol production economically more competitive. Saccharomyces cerevisiae, an efficient ethanol producer, can utilize xylose only when expressing the heterologous genes XYL1 (xylose reductase) and XYL2 (xylitol dehydrogenase). Xylose reductase and xylitol dehydrogenase convert xylose to its isomer xylulose. The gene XKS1 encodes the xylulose-phosphorylating enzyme xylulokinase. In this study, we determined the effect of XKS1 overexpression on two different S. cerevisiae host strains, H158 and CEN.PK, also expressing XYL1 and XYL2. H158 has been previously used as a host strain for the construction of recombinant xylose-utilizing S. cerevisiae strains. CEN.PK is a new strain specifically developed to serve as a host strain for the development of metabolic engineering strategies. Fermentation was carried out in defined and complex media containing a hexose and pentose sugar mixture or a birch wood lignocellulosic hydrolysate. XKS1 overexpression increased the ethanol yield by a factor of 2 and reduced the xylitol yield by 70 to 100% and the final acetate concentrations by 50 to 100%. However, XKS1 overexpression reduced the total xylose consumption by half for CEN.PK and to as little as one-fifth for H158. Yeast extract and peptone partly restored sugar consumption in hydrolysate medium. CEN.PK consumed more xylose but produced more xylitol than H158 and thus gave lower ethanol yields on consumed xylose. The results demonstrate that strain background and modulation of XKS1 expression are important for generating an efficient xylose-fermenting recombinant strain of S. cerevisiae.