INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2019
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IF 3.375
Siquan Xu,Donghui Pan,Yuanfeng Wu,Jingdeng Fan,Ningxin Wu,Lijing Gao,Wenqi Li,Guomin Xiao
The mesoporous SBA-15 has long been used as an adsorbent for the removal of toxic metal ions. Achieving secondary utilize of spent adsorbent is undoubtedly an advisible option for environmental protection and recycling economy. In the present study, phosphoric acid-modified SBA-15 (P-SBA-15) was found to be an available adsorbent, and the composites (Cr3+/P-SBA-15) formed after adsorption of Cr3+ ions have the ability to efficiently catalyze the conversion of xylose and xylan into furfural. The physicochemical properties of the Cr3+/P-SBA-15 composites were characterized, and the effects of various reaction parameters on their catalytic performance were also investigated. Among the Cr3+/P-SBA-15 composites with different Cr3+ contents, the (0.25)Cr3+/P-SBA-15 composite not only achieved excellent 91% and 58% furfural yields from xylose and xylan, but also had almost constant catalytic performance after five cycles. The findings herein provided a reference for achieving high yields of furfural and reuse of spent adsorbents.
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ENERGY & FUELS
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2018
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IF 3.024
Jin Tan,Chenguang Wang,Qi Zhang,Longlong Ma,Minghong He
A novel and efficient method for the use of non-edible cassava to synthesize biofuel precursors with long carbon chains in two steps was proposed. The finally produced precursors were based on the decomposition of cassava and condensation between furans and levulinates. The reaction parameters for levulinate production from cassava were optimized, and the results showed that the highest carbon mole yield of levulinates was up to 51.3% at 473 K, 4.0 MPa N2, and 6.0 h. After that, precursors with yields of 88.0 and 90.5% could be obtained when the mole ratios between furans and levulinates were 1:1 and 2:1, respectively. Characterization of precursors using elemental analysis, 13C nuclear magnetic resonance, gel permeation chromatography, and Fourier transform infrared spectroscopy demonstrated that different and intersecting routes of condensation resulted in the complex components of precursors. Moreover, the mechanism of condensation was proven to excessively depend upon the mole ratio between furans and levulinates in this investigation. This technical route indicates a simple and feasible method to produce renewable biofuel with long carbon chains from cassava directly.
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Energy Science & Engineering
·
2017
·Vol. 5
·期 4
·208-216
·
IF 2.172
Yuan Zhao,Haizhou Lin,Shurong Wang
A novel green reaction system of CO 2 –water–isopropanol has been developed for the production of furfural (FF) from xylose. Initially, a simple CO 2 –water system was investigated, and the results showed that the formation of FF from xylose was greatly enhanced. CO 2 at high pressure could increase the acidity of the reaction system, and thus the FF yield was improved. By raising the reaction temperature, the conversion of xylose was remarkably accelerated in the CO 2 –water–isopropanol system, leading to an acceptable conversion rate (94.41%) and FF yield (55.81%). Addition of an appropriate amount of NaCl further increased the yield to 69.20%. Other carbohydrates (arabinose and xylan) were also tested in the same reaction system and modest results were obtained.
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Molecular Catalysis
·
2024
·
IF 3.9
Xing Gao,Wenna Zhang,Yingying Ruan,Shihao Zhang,Sheng Wei,Yiwen Zhang,Pengfei Liu,Dong Tian,Yihu Dai,Yanhui Yang
The conversion of biomass-based compounds into highly value-added chemicals has received extensive attention in recent years. This work reports the liquid-phase selective hydrogenation and furan ring-rearrangement of furfural (FFL) into cyclopentanone (CPO) and cyclopentanol (CPL) over Pd/Co 4 Al 1 -HTs catalysts and water as the solvent. The specific reaction rate of the optimal catalyst at 160 °C reaches 538 h –1 , and the selectivity of CPO/CPL is 77.5 %. By adopting the ion-exchange and formamide treatment methods, the type of the interlayer anions and interlayer spacing for the CoAl-HTs supports can be regulated, which can affect the state of the supported Pd sites and their catalytic activity and selectivity towards the ring-rearrangement products. Furthermore, the H 2 /D 2 exchange experimental results demonstrate that the presence of the interlayer NO 3 – anions of CoAl-HTs support promotes the activation and dissociation of H 2 , thereby accelerating the hydrogenation of FFL to cyclic compounds.
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Molecular Catalysis
·
2017
·
IF 0
Wanbing Gong,Chun Chen,Haimin Zhang,Yong Zhang,Yunxia Zhang,Guozhong Wang,Huijun Zhao
In this work, N-doped activated carbon supported metallic nickel (Ni/NAC) catalysts were fabricated by two-step calcination method in N 2 atmosphere for liquid-phase hydrogenation of furfural (FAL). It was found that the pyrolysis temperature and amount of melamine as N doping source have important influence on N doping content and type in activated carbon (AC) support, resulting in the subsequently formed Ni nanoparticles on N-doped AC with different sizes and thus affording different catalytic hydrogenation activities. The results demonstrated that using N-doped AC with 1.0 g melamine at 1073 K in N 2 atmosphere as support, the obtained Ni/NAC at 873 K in N 2 atmosphere with Ni nanoparticle sizes of ∼13.1 nm (denoted as Ni/NAC-1-1073) exhibits a N doping content of 3.65 at.% and a surface area of 561.2 m 2 g −1 with a microporous structure. As catalyst for FAL hydrogenation, Ni/NAC-1-1073 demonstrated the best catalytic performance among all investigated catalysts, achieving almost 100% selectivity of tetrahydrofurfuryl alcohol (THFOL) with a complete FAL conversion at 353 K after 3 h reaction, while only 76.7% selectivity of THFOL with a FAL conversion of 86.4% was obtained using Ni/AC catalyst without N doping under the identical experimental conditions. Furthermore, it was found that almost 100% conversion of FAL to furfural alcohol (FOL) can be reached by transfer hydrogenation pathway in 2-proponal solvent using Ni/NAC-1-1073 at 413 K after 5 h reaction, whereas Ni/AC without N doping can only afford 30.2% conversion of FAL to FOL under the same conditions. The superior catalytic performance of Ni/NAC-1-1073 could be ascribed to a synergistic effect of nanosized Ni providing catalytic active sites, suitable N doping content and type in AC to promote catalytic performance, and advantageous structure characteristics of high surface area and porous structure favourable for the exposure of catalytic active sites and mass transport.
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CATALYSIS TODAY
·
2017
·
IF 4.636
Xinli Tong,Linhao Yu,Xuan Luo,Xuli Zhuang,Shengyun Liao,Song Xue
The efficient transformation of furfural (FUR) with aliphatic alcohols to achieve the carbon-chain growth has been developed using a binary Cu-Ce oxide as the catalyst. In the presence of molecular oxygen, the tandem oxidative condensation of FUR with n -propanol is successfully performed, in which an 85.4% conversion of FUR in 95.3% selectivity of 3-(furan-2-yl-)-2-methylacryaldehyde was obtained. The effects of different Cu/Ce ratios and base additives were investigated in detail. As a result, it is found that the CuO-CeO 2 (1: 9) catalyst is optimal and potassium carbonate is a suitable additive. Next, the recycling of CuO-CeO 2 catalyst was tested and there is no obvious activity loss after being reused five times. Moreover, the oxidative condensation of FUR with various aliphatic alcohols including ethanol, isopropanol, n -butanol and n -hexanol was studied where the long chain alcoholic molecule hinders the proceeding of reaction. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the oxidative condensation of FUR with n -propanol-O 2 is proposed.
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CHINESE JOURNAL OF CATALYSIS
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2017
·
IF 2.813
Na Huo,Hong Ma,Xinhong Wang,Tianlong Wang,Gang Wang,Ting Wang,Leilei Hou,Jin Gao,Jie Xu
ABSTRACT From both fundamental and practical perspectives, the production of chemicals from biomass resources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consumption, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxidative esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt(II) phenanthroline complex on MgO at 800 °C under N 2 atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O 2 with reaction at 100 °C for 12 h without a basic additive. The conversion and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt(II) phenanthroline complex on activated carbon or typical basic supports, including NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for production of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C(HCl) that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation product, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only provides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.
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RSC Advances
·
2016
·Vol. 6
·期 79
·75793-75804
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IF 3.289
Haiming Cheng,Huafei Xue,Changqing Hong,Xinghong Zhang
Organic aerogels generally exhibit poor thermal, mechanical and hydrophilic properties, which seriously restrict their large-scale applications. In this study, siliane was introduced into resorcinol-furfural (RF) aerogels due to the enhancement of silicone to thermal stability and hydrophobicity of polymer molecules. Resorcinol-furfural/silicone (Si–RF) hybrid aerogels were synthesized by sol–gel polycondensation of resorcinol, furfural, (3-aminopropyl) triethoxysilane (ATPES) and methyltrimethoxysilane (MTMS), followed by ambient pressure drying (APD). The Si–RF aerogels showed an interpenetrating framework with high mesoporosity. Silicon-containing functional groups were successfully incorporated into the RF aerogels in dehydration reactions. Surface area, characteristic thermal degradation temperature and char yield of the Si–RF aerogels are higher than that of the as-prepared RF aerogels. In order to improve the mechanical properties, carbon fabric reinforced Si–RF aerogel composites were prepared by impregnating a carbon-bonded carbon fiber (CBCF) composite with the hybrid aerogels. The obtained composites possessed a low bulk density (0.309–0.375 g cm−3), high compressive strength (0.759–2.940 MPa for different directions) and low thermal conductivity (0.085–0.136 W (m−1 K−1)). Hydrophobic aerogels were also fabricated by –Si(CH3)3 (trimethylsilyl substituent) modification via immersing fresh Si–RF aerogels in trimethylethoxysilane (TMES)/hexane solution followed by aging and APD. The hydrophobic property was promoted by the concentrations of solutions (water contact angle of about 108–135°), also the thermal stability.
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CHINESE JOURNAL OF CATALYSIS
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2014
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IF 1.552
Wenju Wang,Huiling Li,Junli Ren,Runcang Sun,Jie Zheng,Guangwei Sun,Shijie Liu
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 SnCl 4 was the most effective chloride. The catalytic activity of paired SnCl 4 /LiCl catalysts was much higher than that of the single salt, and when the distribution coefficient ( χ SnCl4 ) 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 °C for 6 h under the optimized reaction conditions.
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ENERGY
·
2024
·
IF 9
Bingbing Qiu,Jicheng Shi,Wei Hu,Yanfang Wang,Donghui Zhang,Huaqiang Chu
Hydrothermal liquefication of biomass to produce high-quality chemicals and liquid fuels is considered as a renewable and sustainable technology. Herein, a one-step hydrothermal method was used to prepare microcrystalline cellulose supported carbon-based catalyst PTA-BC with the activation factor of phosphotungstic acid. It was demonstrated by Py-FTIR, NH 3 -TPD and XPS that PTA-BC is not only rich in functional groups but also contains Brønsted acid sites (hydroxyl groups) and Lewis acid sites (C C, carboxyl groups). After experimental optimization, the optimum yield of furfural obtained from xylose catalyzed by PTA-BC was 81.02% at the reaction temperature of 180 °C and the reaction time of 20 min. The results show that PTA-BC contains –COOH, –OH and C C as catalytic sites and that the synergistic effect of these functional groups. The nature of the reaction solvent, appropriate reaction temperature and residence time are the main reasons for the good catalytic performance. This work provides a promising way for the synthesis of solid acid catalyst, which has a wide application prospect for the production of furfural.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Dayu Sun,Panli Liu,Huijun Liu,Zhixiu Yang,Lijing Gao,Ruiping Wei,Xiaomei Pan,Guomin Xiao
Furfural, a promising biobased platform chemical, can be derived from xylan through an acid-catalyzed dehydration process. However, the yield of furfural in the aqueous phase is often limited by side reactions (furfural degradation). Employing a biphasic solvent system for in situ furfural extraction presents a strategy to mitigate furfural degradation as furfural is more stable in some organic phases, reducing the polymerization with reaction intermediates in the aqueous phase. In this study, a novel energy-efficient process was developed for the enhanced production of furfural from corncob xylan in a biphasic solvent system. A series of niobium-modified SBA-15 solid acid catalysts for furfural production were synthesized and characterized to determine the physical properties, structure, and crystallinity. The toluene/H2O biphasic system was selected to intensify the furfural production and reduce subsequent separation costs. The experimental parameters including niobium doping of catalyst, reaction time, reaction temperature, catalyst input, and xylan input were optimized to obtain high furfural yield. The process model for production and purification of furfural was established based on experimental data, and the results demonstrated that the furfural purification section in the proposed process reduced cold energy consumption by 64.08% and heat energy consumption by 70.29% compared to the conventional process.
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FUEL
·
2024
·
IF 6.7
Renjie Ji,Defu Yin,Yao Chen,Like Ma,Fanglin Lv,Yuhao Zhang,Zhen Jia,Jingyun Zhang,Mingya Liu,Shitao Yu,Yue Liu
A core–shell catalyst mZSM-5@SO 4 2- /mSiO 2 composed of mZSM-5 core and SO 4 2- /mSiO 2 shell was prepared by the soft template method. Core-shell structure could promote the building of Brønsted -Lewis (B-L) acids interface and significantly improve the synergistic effect of B-L. In this paper, the Brønsted/Lewis (B/L) of mZSM-5@SO 4 2- /mSiO 2 was targeted regulating by innovatively introducing Brønsted acid (BA) sites into the shell. The optimal mZSM-5@SO 4 2- /mSiO 2 catalyst (B/L = 0.142) could achieve 72.1 % furfural yield at 140 ℃ for 1 h. In addition, 70.2 % furfural yield could be obtained after the catalyst was recycled and regenerated for 5 times. Combining In-situ IR and 13 C NMR, the reaction path was revealed in detail: xylose was first isomerized to xylulose and then dehydrated to furfural. This paper provides a research idea for the directional regulation of dual active sites of cascade reaction catalysts.
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