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    Chinese Journal of Catalysis
    2014, Vol. 35, No. 5
    Online: 18 April 2014

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    To resolve the challenges from the depletion of fossil energy resources and increase of CO2 emission, getting fuels and chemicals from vast but nonfood renewable biomass by catalysis has been regarded as an attractive and sustainable way. This special issue is a selection of the papers presented at the 2nd International Congress on Catalysis for Biorefineries (CatBior 2013, Dalian, China). One review and 19 research articles are contained, which cover the most important aspects of catalysis in biomass. The readers will find the latest progresses and thoughtful discussion on the development of biomass conversion.

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    Table of Contents
    Table of Contents for VOL.35 No.5
    2014, 35 (5):  0-0. 
    Abstract ( 206 )   PDF (1612KB) ( 448 )  
    Editorial
    Review
    One-pot catalytic conversion of cellulose to ethylene glycol and other chemicals:From fundamental discovery to potential commercialization
    Mingyuan Zheng, Jifeng Pang, Aiqin Wang, Tao Zhang
    2014, 35 (5):  602-613.  DOI: 10.1016/S1872-2067(14)60013-9
    Abstract ( 522 )   [Full Text(HTML)] () PDF (845KB) ( 1188 )  

    The one-pot catalytic conversion of cellulose to ethylene glycol (CEG) is a highly attractive way for biomass utilization to lessen the consumption of fossil energy resources. In this paper, we reviewed the disclosure of the CEG process and the rapid progress in the development of highly efficient and robust catalysts for it. Based on our study of tungstenic catalysts, we discuss the reaction mechanism, in which the reaction routes, catalyst states, and catalytic roles of the tungsten species and hydrogenation sites in the cascade reactions are understood clearly. With future applications in mind, the conversion of raw cellulosic biomass and the strategy to develop an efficient CEG process for commercialization are discussed, and a model where the CEG process is incorporated into a bio-refinery process of acetone-n-butanol-ethanol (ABE) production is presented.

    Articles
    Sorbitol hydrogenolysis to glycols by supported ruthenium catalysts
    Inmaculada Murillo Leo, Manuel Lopez Granados, Jose Luis Garcia Fierro, Rafael Mariscal
    2014, 35 (5):  614-621.  DOI: 10.1016/S1872-2067(14)60086-3
    Abstract ( 328 )   [Full Text(HTML)] () PDF (730KB) ( 770 )  

    Supported Ru catalysts were prepared by wet impregnation to evaluate the role of different oxide supports (Al2O3, SiO2, TiO2, ZrO2) in sorbitol hydrogenolysis to glycols. X-ray diffraction, transmission electron microscopy, hydrogen chemisorption, X-ray photoelectron spectroscopy, and NH3 temperature-programmed desorption were used to characterize the catalysts, which were active in the hydrogenolysis of sorbitol. The support affected both the physicochemical properties and catalytic behavior of the supported Ru particles. The characterization results revealed that the Ru/Al2O3 catalyst has a high surface acidity, partially oxidized Ru species on the surface, and a higher surface Ru/Al atomic ratio, which gave it the highest selectivity and yield to glycols.

    Low-temperature oxidation of guaiacol to maleic acid over TS-1 catalyst in alkaline aqueous H2O2 solutions
    Ji Su, Lisha Yang, Reed Nicholas Liu, Hongfei Lin
    2014, 35 (5):  622-630.  DOI: 10.1016/S1872-2067(14)60039-5
    Abstract ( 418 )   [Full Text(HTML)] () PDF (1181KB) ( 615 )  

    To mitigate the negative environmental impact of greenhouse gas (GHG) emission originated from the use of fossil fuels, the chemical world is switching to utilize renewable biomass resources. Co-producing value-added chemicals is important for an integrated biorefinery to improve economics of biofuels. Lignin derived compounds, e.g. guaiacol, are common by-products of fast pyrolysis of lignocellulosic biomass. In this paper, the feasibility of low-temperature selective oxidation of guaiacol to value-added dicarboxylic acids, e.g. maleic acid, was investigated using titanium silicalite/hydrogen peroxide (TS-1/H2O2) reaction system. Under the reaction conditions (80 ℃ and the initial pH = 13.3), the molar yields of maleic acid from guaiacol were approximately 20%-30%. The effects of catalyst amount, initial pH values, reaction time, and temperature on the yields of maleic acid were investigated. A possible reaction mechanism of TS-1 catalyzed aromatic ring opening was proposed.

    Selective hydrogenolysis of glycerol to propylene glycol on hydroxycarbonate-derived Cu-ZnO-Al2O3 catalysts
    Shuai Wang, Haichao Liu
    2014, 35 (5):  631-643.  DOI: 10.1016/S1872-2067(14)60094-2
    Abstract ( 467 )   [Full Text(HTML)] () PDF (1031KB) ( 843 )  

    Three Cu-ZnO-Al2O3 catalysts with similar compositions were prepared by homogeneous coprecipitation (CZA-HP), deposition-precipitation (CZA-DP), and conventional coprecipitation (CZA-CP). A Cu-ZnO catalyst was also prepared by homogeneous coprecipitation (CZ-HP) for reference. X-ray diffraction results showed that the degree of mixing of Cu2+, Zn2+, and Al3+ ions in the Cu-Zn-Al hydroxycarbonate precursor followed the order of CZA-DP < CZA-HP < CZA-CP. A more homogeneous aluminum distribution and intimate contact between Al2O3 and ZnO led to smaller CuO and ZnO crystallites in the CuO-ZnO-Al2O3 composite oxides, and consequently smaller Cu and ZnO crystallites in the final Cu-ZnO-Al2O3 catalysts. However, the intimate ZnO-Al2O3 contact hindered the interaction between Cu and ZnO in the Cu-ZnO-Al2O3 catalysts. As a result of these effects of Al2O3, for the samples other than CZA-CP, the Cu particles on CZA-HP showed the highest redox activity, which was characterized by N2O chemisorption-H2 temperature-programmed reduction. These catalysts catalyzed glycerol hydrogenolysis to propylene glycol with high selectivities above 90% at 30% glycerol conversion (473 K and 6.0 MPa H2). Their activities normalized per exposed surface Cu atom to give turnover frequencies increased in the order CZA-DP < CZA-CP < CZ-HP < CZA-HP, which was the order of the redox ability of the Cu particles. The addition of alumina increased the stability of Cu-ZnO catalysts. After six cycles (6 h per run), the activity of CZ-HP decreased by 45% accompanied by an increase of Cu crystallite size from 13.2 to 45.2 nm, while that of CZA-HP decreased only by 10% with an increase of the Cu crystallite size from 8.3 to 19.0 nm. These results demonstrated the promoting effects of Al2O3 on the activity and stability of Cu-ZnO catalysts derived from the hydroxycarbonates.

    Sulfonic acid heterogeneous catalysts for dehydration of C6-monosaccharides to 5-hydroxymethylfurfural in dimethyl sulfoxide
    Gabriel Morales, Juan A. Melero, Marta Paniagua, Jose Iglesias, Blanca Hernández, María Sanz
    2014, 35 (5):  644-655.  DOI: 10.1016/S1872-2067(14)60020-6
    Abstract ( 295 )   [Full Text(HTML)] () PDF (783KB) ( 650 )  

    Sulfonic acid-functionalized heterogeneous catalysts have been evaluated in the catalytic dehydration of C6 monosaccharides into 5-hydroxymethylfurfural (HMF) using dimethyl sulfoxide (DMSO) as solvent. Sulfonic commercial resin Amberlyst-70 was the most active catalyst, which was ascribed to its higher concentration of sulfonic acid sites as compared with the other catalysts, and it gave 93 mol% yield of HMF from fructose in 1 h. With glucose as the starting material, which is a much more difficult reaction, the reaction conditions (time, temperature, and catalyst loading) were optimized for Amberlyst-70 by a response surface methodology, which gave a maximum HMF yield of 33 mol% at 147 ℃ with 23 wt% catalyst loading based on glucose and 24 h reaction time. DMSO promotes the dehydration of glucose into anhydroglucose, which acts as a reservoir of the substrate to facilitate the production of HMF by reducing side reactions. Catalyst reuse without a regeneration treatment showed a gradual but not very significant decay in catalytic activity.

    Levulinic acid hydrogenolysis on Al2O3-based Ni-Cu bimetallic catalysts
    Iker Obregón, Eriz Corro, Urko Izquierdo, Jesus Requies, Pedro L. Arias
    2014, 35 (5):  656-662.  DOI: 10.1016/S1872-2067(14)60051-6
    Abstract ( 376 )   [Full Text(HTML)] () PDF (472KB) ( 711 )  

    Inexpensive γ-alumina-based nickel-copper bimetallic catalysts were studied for the hydrogenolysis of levulinic acid, a key platform molecule for biomass conversion to biofuels and other valued chemicals, into γ-valerolactone as a first step towards the production of 2-methyltetrahydrofurane. The activities of both monometallic and bimetallic catalysts were tested. Their textural and chemical characteristics were determined by nitrogen physisorption, elemental analysis, temperature-programmed ammonia desorption, and temperature-programmed reduction. The monometallic nickel catalyst showed high activity but the highest by-product production and significant amounts of carbon deposited on the catalyst surface. The copper monometallic catalyst showed the lowest activity but the lowest carbon deposition. The incorporation of the two metals generated a bimetallic catalyst that displayed a similar activity to that of the Ni monometallic catalyst and significantly low by-product and carbon contents, indicating the occurrence of important synergetic effects. The influence of the preparation method was also examined by studying impregnated-and sol-gel-derived bimetallic catalysts. A strong dependency on the preparation procedure and calcination temperature was observed. The highest activity per metal atom was achieved using the sol-gel-derived catalyst that was calcined at 450 ℃. High reaction rates were achieved; the total levulinic acid conversion was obtained in less than 2 h of reaction time, yielding up to 96% γ-valerolactone, at operating temperature and pressure of 250 ℃ and 6.5 MPa hydrogen, respectively.

    Glycerol chlorination in a gas-liquid semibatch reactor:New catalysts for chlorohydrin production
    R. Vitiello, V. Russo, R. Turco, R. Tesser, M. Di Serio, E. Santacesaria
    2014, 35 (5):  663-669.  DOI: 10.1016/S1872-2067(14)60069-3
    Abstract ( 221 )   [Full Text(HTML)] () PDF (496KB) ( 964 )  

    Glycerol from biodiesel production can be an important industrial feedstock for chemical commodities as it can be used in the food, cosmetic, pharmaceutical and tobacco industries. However, crude glycerol derived from biodiesel production has a low value because of impurities. The purification of this glycerol into a high grade involves high costs and is not economically feasible for small and medium size plants. The glycerol conversion into chlorohydrins was studied using new homogeneous catalysts and hydrochloric acid as chlorination agent. This is an interesting alternative route to epichlorohydrin and then to epoxy resins. The behavior of two series of homologous catalysts, glycolic acid series (glycolic acid, di-glycolic acid and thio-glycolic acid) and amminoacid series (glutamic acid, aspartic acid and cysteine), were investigated for their activity and selectivity. Glycolic acids were more active than amminoacids. The pKa values had a strong influence on selectivity (mono-chlorohydrins/di-chlorohydrins) for the amminoacid series, which was not observed for the glycolic acids. A kinetic model and reaction mechanism developed in a previous work were used for interpreting the kinetic runs.

    Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina
    Jerrik Mielby, Raju Poreddy, Christian Engelbrekt, Søren Kegnæs
    2014, 35 (5):  670-676.  DOI: 10.1016/S1872-2067(14)60033-4
    Abstract ( 307 )   [Full Text(HTML)] () PDF (783KB) ( 701 )  

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt% Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H2 in the gas phase. The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis.

    Influence of pretreatment on the catalytic performance of Ru/SBA-15 catalysts for glycerol hydrogenolysis
    Yuming Li, Lan Ma, Huimin Liu, Dehua He
    2014, 35 (5):  677-683.  DOI: 10.1016/S1872-2067(14)60032-2
    Abstract ( 368 )   [Full Text(HTML)] () PDF (917KB) ( 607 )  

    Ru/SBA-15 catalysts were prepared by impregnation and were pretreated under different conditions, and were characterized by N2 adsorption-desorption, X-ray diffraction, CO chemisorption, transmission electron microscopy, and the reaction of glycerol hydrogenolysis. The catalyst calcined in air had larger Ru particles, while the direct reduction of the catalysts with H2 without air pre-calcination made the Ru particles dispersed well. As the H2 reduction temperature increased, the Ru dispersion decreased. The turnover frequency (TOF) of the catalysts increased as the Ru dispersion decreased, indicating that Ru/SBA-15 catalyzed glycerol hydrogenolysis is a structure sensitive reaction.

    The production of light olefins by catalytic cracking of the microalga Isochrysis zhanjiangensis over a modified ZSM-5 catalyst
    Xinglong Dong, Song Xue, Jinling Zhang, Wei Huang, Jiannan Zhou, Zhaoan Chen, Danhua Yuan, Yunpeng Xu, Zhongmin Liu
    2014, 35 (5):  684-691.  DOI: 10.1016/S1872-2067(14)60026-7
    Abstract ( 300 )   [Full Text(HTML)] () PDF (501KB) ( 650 )  

    This study investigated the catalytic cracking of the microalga Isochrysis zhanjiangensis over a modified ZSM-5 catalyst with the aim of producing C2-C4 light olefins. Compared with the thermal cracking process, the catalytic cracking of this microalga displayed higher selectivity for and greater yield of these olefins. The catalytic cracking of extracted lipids and the corresponding residues of the microalga was also examined, and the results showed that the lipids could be efficiently converted to light olefins. The catalytic cracking of lipids extracted by different solvents demonstrated that neutral lipids gave the highest yield of light olefins at 36.7%. The yields of light olefins obtained from catalytic cracking of the extraction residues were much lower than the yields obtained from lipids, and thus the lipids, especially the neutral lipids, are the primary contributors to the generation of light olefins. Isochrysis zhanjiangensis with an elevated neutral lipid content will therefore give the highest yield of light olefins through catalytic cracking.

    Hydrogenolysis of sorbitol to glycols over carbon nanofibers-supported ruthenium catalyst:The role of base promoter
    Jinghong Zhou, Guocai Liu, Zhijun Sui, Xinggui Zhou, Weikang Yuan
    2014, 35 (5):  692-702.  DOI: 10.1016/S1872-2067(14)60083-8
    Abstract ( 337 )   [Full Text(HTML)] () PDF (1008KB) ( 579 )  

    Sorbitol hydrogenolysis over carbon nanofibers-supported Ru (Ru/CNFs) was carried out with different bases (NaOH, KOH, Mg(OH)2, Ba(OH)2, and CaO) to investigate the role of base promoter. The results indicated that all the bases used significantly enhanced the sorbitol conversion while the glycol selectivities varied with the base type and amount. CaO was the best base in terms of glycol selectivity for two reasons. CaO provided OH- for the base-promoted cleavage of C-C bonds, while it also supplied Ca2+ for complexation with the intermediate aldehydes, thus affecting the reaction pathways. We identified an optimum ratio among sorbitol concentration, Ru/CNFs catalyst, and CaO to achieve favorable glycol selectivities in sorbitol hydrogenolysis. Reaction pathways for sorbitol hydrogenolysis into glycols in aqueous solution in the presence of CaO have been proposed based on the mechanistic study.

    Nanocoating of magnetic cores with sulfonic acid functionalized shells for the catalytic dehydration of fructose to 5-hydroxymethylfurfural
    Xiaochen Zhang, Min Wang, Yehong Wang, Chaofeng Zhang, Zhe Zhang, Feng Wang, Jie Xu
    2014, 35 (5):  703-708.  DOI: 10.1016/S1872-2067(12)60739-6
    Abstract ( 292 )   [Full Text(HTML)] () PDF (637KB) ( 787 )  

    A magnetically recyclable acid catalyst composed of an Fe3O4 core and sulfonic acid functionalized silica shell has been prepared using the reverse microemulsion method. The Fe3O4 core was coated with a phenyl modified silica shell nanolayer, and the phenyl groups were subsequently sulfonated to generate a solid sulfonic acid catalyst. The resulting acid catalyst showed higher activity than the conventional A-15 catalyst and comparable activity to several homogeneous sulfonic acid catalysts for the dehydration of fructose to 5-hydroxymethylfurfural (HMF). This process gave a fructose conversion of 99% with an HMF yield of 82% following 3 h in dimethylsulfoxide at 110 ℃. Furthermore, the catalyst could be magnetically separated and recycled several times without losing its activity.

    Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5
    Shurong Wang, Qinjie Cai, Xiangyu Wang, Li Zhang, Yurong Wang, Zhongyang Luo
    2014, 35 (5):  709-722.  DOI: 10.1016/S1872-2067(14)60046-2
    Abstract ( 370 )   [Full Text(HTML)] () PDF (668KB) ( 807 )  

    Acids and ketones in biomass pyrolysis oil (bio-oil) can be readily cracked to produce hydrocarbons. They can also be enriched in the distilled fraction using molecular distillation techniques. To simulate the actual composition of the distilled fraction, the co-cracking performance of mixtures of hydroxypropanone, cyclopentanone, and acetic acid with ethanol in a fixed-bed reactor over an HZSM-5 catalyst was studied. The influences of reaction temperature and pressure on the reactant conversion, selectivity, and composition of the oil phase were investigated. At a low reaction temperature of 340 ℃, the conversions of acetic acid and ethanol were as low as 67.9% and 74.4%, respectively, and the oil phase had a low hydrocarbon content of 59.8%, with large amounts of oxygenated byproducts. Cracking under atmospheric pressure also generated a low-quality oil phase with a very low selectivity of only 10.8%. Increasing the reaction temperature promoted reactant conversion and improved the deoxygenation efficiency, whereas increasing the reaction pressure significantly promoted hydrocarbon production. The optimum conditions for biogasoline production were 400 ℃ and 2 MPa. Under these conditions, the reactant conversion reached 100% and the oil phase selectivity was 31.5 wt%. This oil phase consisted entirely of hydrocarbons, 91.5 wt% of which were aromatic hydrocarbons, indicating that the HZSM-5 catalyst had high activity for deoxygenation and aromatization reactions during cracking. In addition, characterization of the spent catalysts and stability tests showed that the catalyst was deactivated after a long reaction time. However, the catalytic activity was recovered by catalyst regeneration.

    Facile preparation of Sn-β zeolites by post-synthesis (isomorphous substitution) method for isomerization of glucose to fructose
    Min Liu, Songyan Jia, Changzeng Li, Anfeng Zhang, Chunshan Song, Xinwen Guo
    2014, 35 (5):  723-732.  DOI: 10.1016/S1872-2067(14)60071-1
    Abstract ( 335 )   [Full Text(HTML)] () PDF (677KB) ( 862 )  

    Sn-β zeolites were facilely synthesized by a post-synthesis method consisting of two steps, i.e., heteroatom removal and isomorphous substitution by reaction with SnCl4. This significantly shortened the Sn-β zeolite preparation time from the previously reported 40 d to less than 1 d. It was shown that Sn-β samples prepared using the post-synthesis method had higher Sn contents than that prepared using a hydrothermal method. The as-synthesized Sn-β zeolites were tested in the isomerization of glucose to fructose in aqueous media. The effects of reaction temperature, reaction time, catalyst amount, solvent, and halide additive on the isomerization reaction over Sn-Al-β zeolites were studied in detail. Under the optimized conditions, the yield of fructose reached a maximum of ~43%. The catalysts can be reused without loss of activity after regeneration by calcination.

    Selective hydrogenation of D-glucose to D-sorbitol over Ru/ZSM-5 catalysts
    Xingcui Guo, Xicheng Wang, Jing Guan, Xiufang Chen, Zhangfeng Qin, Xindong Mu, Mo Xian
    2014, 35 (5):  733-740.  DOI: 10.1016/S1872-2067(14)60077-2
    Abstract ( 374 )   [Full Text(HTML)] () PDF (893KB) ( 958 )  

    Ru particles were introduced into the zeolite ZSM-5 (MFI) by either a conventional impregnation method or a one-step template-free process. The resultant materials were characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, NH3 and CO2 temperature-programmed desorption. The results indicated that the Ru species in ZSM-5 catalysts prepared via the latter approach (designated as Ru/ZSM-5-TF) were highly dispersed in the ZSM-5 framework structure and this material exhibited high catalytic performance during the hydrogenation of D-glucose to D-sorbitol. The conversion of D-glucose was as high as 99.6% with D-sorbitol selectivity reaching 99.2%, exceeding the performance of Ru/ZSM-5 catalysts prepared by the conventional impregnation method with microporous or desilicated ZSM-5 supports. More importantly, this catalyst showed high stability against leaching and poisoning and could be reused several times. The extensive dispersion of the Ru species, strong interaction between the Ru species and the ZSM-5, and the suitable surface acidity-basicity balance of the Ru/ZSM-5-TF were all critical factors leading to excellent catalytic behavior and stability.

    An efficient process for dehydration of xylose to furfural catalyzed by inorganic salts in water/dimethyl sulfoxide system
    Wenju Wang, Huiling Li, Junli Ren, Runcang Sun, Jie Zheng, Guangwei Sun, Shijie Liu
    2014, 35 (5):  741-747.  DOI: 10.1016/S1872-2067(14)60031-0
    Abstract ( 331 )   [Full Text(HTML)] () PDF (651KB) ( 726 )  

    An efficient homogeneous catalytic process was developed for the dehydration of xylose to furfural using inorganic salts as catalysts in a water/dimethyl sulfoxide (DMSO) system under mild condition. The effects of the types of inorganic salts were compared. The results showed that chlorides had higher catalytic performance than other salts, and SnCl4 was the most effective chloride. The catalytic activity of paired SnCl4/LiCl catalysts was much higher than that of the single salt, and when the distribution coefficient (χSnCl4) was 0.8, the maximum furfural yield was 56.9%. The effects of the reaction conditions on the furfural yield were also investigated. The highest furfural yield, 63.0%, was achieved at 130 ℃ for 6 h under the optimized reaction conditions.

    Hydrodeoxygenation of palm oil to hydrocarbon fuels over Ni/SAPO-11 catalysts
    Qiying Liu, Hualiang Zuo, Qi Zhang, Tiejun Wang, Longlong Ma
    2014, 35 (5):  748-756.  DOI: 10.1016/S1872-2067(12)60710-4
    Abstract ( 377 )   [Full Text(HTML)] () PDF (886KB) ( 1914 )  

    Small particles of SAPO-11 with large surface area and mesoporosity were synthesized hydrothermally. Ni/SAPO-11 catalysts with different Ni loadings were prepared by incipient wetness impregnation, and their physicochemical properties were characterized by X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption, NH3 temperature-programmed desorption, Thermogravimetric, and H2 chemisorption. In the Ni impregnation of SAPO-11, the mesopores of SAPO-11 accommodated the Ni particles and give good dispersions, but with the partial blocking of some micropores. In the hydrodeoxygenation of palm oil, the production of liquid alkanes depends on the competition between hydrodeoxygenation and decarbonylation pathways via the corresponding carboxylic acid intermediates. The weak and medium acidity of SAPO-11 and a good match of the Ni and SAPO-11 functions in the Ni/SAPO-11 catalysts decreased the cracking of primary long chain alkanes and gave a high liquid alkane yield of 70 wt% and isomerization selectivity of >80 mol%.

    Basic ionic liquids promoted the synthesis of glycerol 1,2-carbonate from glycerol
    YuxuanYi, Yue Shen, Jiankui Sun, Bo Wang, Feng Xu, Runcang Sun
    2014, 35 (5):  757-762.  DOI: 10.1016/S1872-2067(14)60036-X
    Abstract ( 421 )   [Full Text(HTML)] () PDF (482KB) ( 1025 )  

    Glycerol has been subjected to a transesterification process with dialkyl carbonate to generate glycerol 1,2-carbonate (GC) using different ionic liquids as catalysts under solvent-free conditions. The basic ionic liquids 1-butyl-3-methylimidazolium imidazolium ([Bmim]Im), 1-butyl-3-methylimidazolium hydroxide ([Bmim]OH), 1-allyl-3-methylimidazolium imidazolium ([Amim]Im), and 1-allyl-3-methylimidazolium hydroxide ([Amim]OH) worked well as catalysts compared with acidic ionic liquid and inorganic basic catalysts. Subsequent optimization of the reaction conditions using [Bmim]Im as a catalyst led to 98.4% glycerol conversion and up to 100% GC selectivity at 70 ℃ under ambient pressure. The recovery and reuse of these ionic liquids were also satisfactory. [Bmim]Im could be reused three times (i.e., 92.0% glycerol conversion and near 100% GC selectivity). This method exhibited several special features including a simple product isolation procedure, high product yield, exclusive selectivity, and mild conditions, as well as avoiding the use of any toxic catalysts.

    Enzymatic hydrolysis enhancement of corn lignocellulose by supercritical CO2 combined with ultrasound pretreatment
    Jianzhong Yin, Liudan Hao, Wen Yu, Enjun Wang, Mengjiao Zhao, Qinqin Xu, Yifan Liu
    2014, 35 (5):  763-769.  DOI: 10.1016/S1872-2067(14)60040-1
    Abstract ( 302 )   [Full Text(HTML)] () PDF (1065KB) ( 686 )  

    Supercritical carbon dioxide (scCO2) combined with an ultrasound method using 15-25 MPa and the temperature range of 120-170 ℃ for 0.5-4 h was proposed as a pretreatment for corn cob and corn stalk with moisture contents of 50%. The results showed that both scCO2 pretreatment and scCO2 combined with ultrasound pretreatment could improve the total reducing sugar yields of the two materials. Enzymatic hydrolysis of both corn cob and corn stalk sugar using scCO2 pretreatment was increased by 50% and 29.8% compared with the control samples, respectively, while they were increased by 75% and 13.4%, respectively, using the scCO2 combined with ultrasound pretreatment under our experimental conditions. Following treatment from the two pretreatment processes, X-ray diffraction results indicated no significant change in crystallinity of the two materials. However, scanning electron microscopy images demonstrated that the microscopic structure of lignocellulose changed considerably and the surface area of lignocellulose increased significantly.

    Application of surface-modified carbon powder in microbial fuel cells
    Gaixiu Yang, Yongming Sun, Zhenhong Yuan, Pengmei Lü, Xiaoying Kong, Lianhua Li, Guanyi Chen, Tianhong Lu
    2014, 35 (5):  770-775.  DOI: 10.1016/S1872-2067(14)60023-1
    Abstract ( 290 )   [Full Text(HTML)] () PDF (492KB) ( 594 )  

    The catalytic activity of surface-modified carbon powder, Vulcan XC-72R (XC), for the oxygen reduction reaction (ORR) at an air cathode in a microbial fuel cell (MFC) has been investigated. The effects of treatment with different chemicals such as nitric acid and ammonia on the chemical characteristics of XC were studied. The catalysts were characterized by Fourier transform infrared spectroscopy (FTIR), Boehm titration, and X-ray photoelectron spectroscopy. FTIR analysis showed that the functional groups of the materials were changed by chemical treatment, with nitric acid causing the introduction of oxygen-containing groups, and ammonia leading to the introduction of nitrogen-containing groups. Electrochemical measurements of MFCs containing various modified carbon materials as ORR catalysts were performed, and the results showed that chemically modified carbon materials are promising catalysts in MFCs.

    Author Index
    2014, 35 (5):  776-776. 
    Abstract ( 100 )   [Full Text(HTML)] () PDF (227KB) ( 173 )