JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2014
·Vol. 90
·期 3
·415-422
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IF 2.494
Yanping Chen,Yiming Xu,Dang-guo Cheng,Yingcai Chen,Fengqiu Chen,Xiaoyong Lu,Yiping Huang,Songbo Ni
BACKGROUND The synthesis of C 2 –C 4 hydrocarbons from coal or biomass-derived syngas has received increasing attention because of the resource constraints of petroleum. The present study explores direct production of hydrocarbons from syngas over bifunctional catalyst containing methanol synthesis catalyst CuO–ZnO–Al 2 O 3 (CZA) and SAPO-34 zeolite. RESULTS The synthesis of C 2 –C 4 hydrocarbons from syngas was investigated over CZA/SAPO-34 bifunctional catalyst at temperatures ranging from 240 to 440°C. The results indicate that higher temperatures aggregate Cu metal and lead to the deactivation of CZA. The predominant products are dimethyl ether (DME) and methanol at temperatures from 280 to 360°C and a small amount of hydrocarbons are found due to the deactivation of SAPO-34 caused by a type of coke named ‘inert coke’. While 96.5% selectivity of C 2 –C 4 hydrocarbons in products of all hydrocarbons can be obtained at 400°C with less coke named ‘active coke’. CONCLUSION Reaction temperatures have significant effect on the selectivity of C 2 –C 4 hydrocarbons and coke species of SAPO-34. The ‘active coke’ of poly methyl-substituted benzene/naphthalene (MB/MN) acts both as an intermediate and as coke deposition. The ‘inert coke’ of poly methyl-substituted adamantine (MA) and other groups-substituted benzene/naphthalene acts only as coke depositions. Comprehensive consideration of the characteristics of this bifunctional catalyst, shows that a moderate temperature for C 2 –C 4 hydrocarbons synthesis from syngas might be approximately 400°C. © 2014 Society of Chemical Industry
研究领域:
化学工程
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2019
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IF 4.084
Mi Yan,Jianyong Liu,Dwi Hantoko,Ekkachai Kanchanatip,Nurak Grisdanurak,Yi Cai,Zengliang Gao
This paper presents the results from experimental study of syngas production by catalytic cracking of tar in wastewater under supercritical condition . Ni/Al 2 O 3 catalysts were prepared via the ultrasonic assisted incipient wetness impregnation on activated alumina , and calcined at 600 °C for 4 h. All catalysts showed mesoporous structure with specific surface area in a range of 146.6–215.3 m 2 /g. The effect of Ni loading (5–30 wt%), reaction temperature (400–500 °C), and tar concentration (0.5–7 wt%) were systematically investigated. The overall reaction efficiency and the gas yields, especially for H 2 , were significantly enhanced with an addition of Ni/Al 2 O 3 catalysts. With 20%Ni/Al 2 O 3 , the H 2 yield increased by 146% compared to the non-catalytic experiment. It is noteworthy that the reaction at 450 °C with the addition of 20%Ni/Al 2 O 3 had a comparable efficiency to the reaction without catalyst at 500 °C. The maximum H 2 yield of 46.8 mol/kg tar was achieved with 20%Ni/Al 2 O 3 at 500 °C and 0.5 wt% tar concentration. The catalytic performance of the catalysts gradually decreased as the reuse cycle increased, and could be recovered to 88% of the fresh catalyst after regeneration. 20%Ni/Al 2 O 3 has a potential to improve H 2 production, as well as a good reusability . Thus, it is considered a promising catalyst for energy conversion of tar in wastewater.
研究领域:
能源化学
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环境工程
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2018
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IF 3.956
Qilei Yang,Ang Cao,Na Kang,Kang An,Zhao-Tie Liu,Yuan Liu
The catalyst for direct ethanol synthesis (DES) from syngas was investigated in this work, which is Co/La 2 O 3 -doped La 4 Ga 2 O 9 . The catalyst was prepared by using LaCo 1−x Ga x O 3 with perovskite phase as the precursor to intensify the interaction in the elements of Co, La and Ga. The catalysts were characterized by using XRD , H 2 -TPR, TEM , EDS, XPS , BET, ICP and TG techniques. This catalyst showed high selectivity to ethanol and excellent stability including excellent resistance to sintering and carbon deposition . It seems that the ethanol is generated in the interface between metallic Co and La 4 Ga 2 O 9 , and in the interface cobalt would be positively charged due to the interaction between Co nanoparticles and La 4 Ga 2 O 9 . The results and the related discussions indicate that Co/La 2 O 3 -doped La 4 Ga 2 O 9 catalyst is a promising catalyst for DES from syngas. Graphical abstracts.
研究领域:
催化
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化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2017
·Vol. 11
·期 4
·613-623
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IF 1.712
Tang Honggui,Li Shuangshuang,Gong Dandan,Guan Yi,Liu Yuan
Carbon deposition and sintering of active components such as nano particles are great challenges for Ni-based catalysts for CO methanation to generate synthetic natural gas from syngas. Facing the challenges, bimetallic catalysts with different Fe content derived from layered double hydroxide containing Ni, Fe, Mg, Al elements were prepared by co-precipitation method. Nanoparticles of Ni-Fe alloy were supported on mixed oxides of aluminium and magnesium after calcination and reduction. The catalysts were characterized by Brunner-Emmett-Teller (BET), X-ray diffraction, hydrogen temperature programmed reduction, inductively coupled plasma, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric techniques, and their catalytic activity for CO methanation was investigated. The results show that the Ni-Fe alloy catalysts exhibit better catalytic performance than monometallic catalysts except for the Ni4Fe-red catalyst. The Ni2Fe-red catalyst shows the highest CO conversion (100% at 260–350 °C), as well as the highest CH 4 selectivity (over 95% at 280–350 °C), owing to the formation of Ni-Fe alloy. In stability test, the Ni2Fe-red catalyst exhibits great improvement in both anti-sintering and resistance to carbon formation compared with the Ni0Fe-red catalyst. The strong interaction between Ni and Fe element in alloy and surface distribution of Fe element not only inhibits the sintering of nanoparticles but restrains the formation of Ni clusters.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
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2022
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IF 8.035
Caixia Zhu,Kaizhuang Xu,Yuan Fang,Qian Lv,Kun Jiang,Huibo Zhao,Yang Chen,Peng Wang,Hua Yang,Lizhi Wu,Yu Tang,Li Tan
The direct synthesis of ethanol from syngas is a promising way in the field of clean and efficient use of fossil fuel, but it still suffers from insufficient ethanol selectivity and understanding of active sites. In this work, the Rh-based catalyst with Ce as promoter and ZrO 2 as carrier exhibits excellent catalytic performance, showing the selectivity of ethanol toward 24.3 %. Moreover, the yield of methane decreases to 4.8 %, and the formation of CO 2 is inhibited to a certain degree by tuning the active sites. The carrier is changed by doping Ce into the ZrO 2 lattice, which assists to form the Rh δ+ active sites. The synergetic effect of Ce and Zr is important to influence the state of Rh species in the catalysts, leading to the differences in the CO hydrogenation process. On the other hand, the Rh δ+ active sites are also stabilized by promoted surface oxygen vacancies in the 2.0Rh5.0Ce-ZrO 2 catalyst. The high-activity catalyst with Rh δ+ active sites will be helpful to understand the real active sites of Rh-based catalysts for ethanol synthesis from syngas, thereby guiding further design of the related catalyst with high performance to meet the industrial demand in syngas converting to ethanol.
研究领域:
催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
TOPICS IN CATALYSIS
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2022
·Vol. 66
·期 1
·262-274
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IF 2.781
Pham Cham Q.,Nguyen Van-Phuoc,Van Thuan Tran,Phuong Pham T.T.,Pham Phuong T.H.,Trinh Thanh H.,Nguyen Tung M.
Syngas, a mixture of carbon monoxide and hydrogen, is widely used in electricity, synthetic chemicals, and fuels productions. Syngas can be obtained from a chemical reaction between methane and carbon dioxide that are commonly found in biogas. In this study, a simulated mixture of biogas containing CH 4 :CO 2 = 1:1 (mol/mol) was used as the feedstock. Different nickel-based catalysts supported on TiO 2 , MgO, KIT-6, and Al 2 O 3 have been prepared through the dry impregnation method with a fixed Ni dosage of 10 wt%. All samples were characterized by modern techniques including XRD, BET, H 2 -TPR, CO 2 -TPD, TPO, and TEM. It was found that the metal-support interaction played a critical role in metal dispersibility and reducibility of catalyst precursors. During the methane dry reforming, catalyst basicity is a crucial factor facilitating the adsorption and activation of carbon dioxide. The highest activity was achieved over 10Ni/Al 2 O 3 with the methane conversion of 73.2% and carbon dioxide conversion of 86.9%. Furthermore, the effects of support properties on the catalyst stability were studied. Nature of support especially basicity plays an important role on the deposition of carbon over the active sites. The Ni/Al 2 O 3 with good nickel dispersibility, affordable metal-support interaction, reasonable basicity was reported the most stable without any significant deactivation after 6 h reaction. Finally, the catalyst design strategy for the DRM was proposed.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
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2021
·Vol. 13
·期 13
·3184-3197
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IF 5.686
Chao Huang,Can Zhu,Mingwei Zhang,Yongwu Lu,Qianhao Wang,Heming Qian,Jiangang Chen,Kegong Fang
Graphical Synergetic effect : The physically mixed CuCoAl|t-ZrO 2 multifunctional catalyst could achieve superior selectivity towards alcohols while simultaneously inhibiting the generation of hydrocarbons from CO hydrogenation. Selective synthesis of higher alcohols from syngas is promising but remains challenging owing to the low stability and selectivity towards higher alcohols. Here we introduce a CuCoAl|t-ZrO 2 (t denotes tetragonal crystal phase) multifunctional catalyst that can achieve an alcohol selectivity of 64.8 % with 79.6 % C 2+ OH, and a total selectivity of alcohols and olefins to 81.7 %. The proper proximity was tuned to increase selectivity towards alcohols and decrease the selectivity towards hydrocarbons. The lower surface [H*]/[C*] ratio due to the stronger basic sites of the CuCoAl|t-ZrO 2 limited alkyl (CH x ) species hydrogenation, and promoted CO insertion and carbon chain growth, resulting in improving the alcohols selectivity. Meanwhile, the weaker adsorption of bridge-type adsorbed CO and the lower decomposition rate of multi-bonded adsorbed CO over CuCoAl|t-ZrO 2 inhibited hydrocarbon generation. The selective promotion of the reaction route via the synergetic effect between CuCoAl and t-ZrO 2 was proposed to boost higher alcohols selectivity. This work may aid the rational design of effective multifunctional catalyst with synergistic effects for tuning selectivity.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
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2024
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IF 3.8
Pengchao Ren,Zhenzhou Zhang,Tingting Hu,Zhihui Fan,Shanshan Dang,Sifan Cheng,Weifeng Tu,Yi-Fan Han
Graphical The apparent rate coefficients for CH 3 OH synthesis from CO hydrogenation are a single-valued function of the CO 2 -to-CO ratio in the contacting gas phase, because this ratio determines the extent of surface oxidation of Ce 2 O 3 to CeO 2 , the relative abundance of surface Ce 3+ , and in turn the density of Cu 0 -Ce 3+ sites pair on the working Cu/CeO 2 catalyst. This study investigated the dynamic structure of a working Cu/CeO 2 catalyst and its catalytic consequences for CH 3 OH synthesis via CO hydrogenation by kinetics, high-precise chemical titration, and a series of in situ X-ray spectroscopies. We have revealed that the apparent rate coefficients for CH 3 OH synthesis from CO hydrogenation are a single-valued function of the CO 2 -to-CO ratio in the contacting gas phase. This ratio determines the extent of surface oxidation of Ce 2 O 3 to CeO 2 , the relative abundance of surface Ce 3+ and Ce 4+ sites, and in turn, the density of Cu 0 -Ce 3+ sites pair on the working Cu/CeO 2 catalyst, although the chemical state of Cu and elemental distribution of both Cu and Ce were insensitive to the ratio. The reactivity of CH 3 OH formation and the Cu 0 -Ce 3+ sites decrease monotonously with an increase in the CO 2 -to-CO ratio. The direct connection of the reactivity and the oxidant-to-reductant ratio appears to be general for heterogeneous catalysis, for which the oxidant oxidizes metal atoms. In contrast, the reductant scavenges surface oxygen atoms, thus dictating the density of surface sites and their thermodynamic activities.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CARBON
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2024
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IF 10.5
Shide Wu,Yifei Zhang,Dan Ping,Yapeng Li,Wan Li,Shuqing Liu,Di Wu,Shiwen Wang,Xuzhao Yang,Guanglu Han,Dongjie Guo,Shaoming Fang
Developing efficient electrocatalysts for CO 2 electroreduction to syngas with a specific H 2 /CO ratio over a wide potential window is desperately required but still challenging. In this work, a series of dual-site catalysts composed of iron phthalocyanine (FePc) and ∼18 nm Cobalt nanoparticles (Co NPs) anchored on N-doped carbon matrix has been constructed from zeolitic imidazolate framework-67 (ZIF-67). Benefiting from the synergistic effect of FePc and Co NPs, the derived FePc/Co@N–C catalyst shows impressive capability for CO 2 electrolysis to syngas. By varying the pyrolysis temperatures (600–800 °C) of ZIF-67 and the mass ratio of Co@N–C to FePc (1–3), an adjustable H 2 /CO ratio of 2–4 is obtained, and the value can be maintained stable within a potential window of −0.66 to −0.86 V vs . RHE in an H-type cell. Moreover, this electrocatalyst exhibits favorable stability without distinct performance decay. When conducted in a flow cell, an enhanced catalytic activity is demonstrated with an industrial current density (>100 mA cm −2 ) at −0.8 V vs . RHE and a steady H 2 /CO ratio of 2 from −0.4 to −0.6 V vs . RHE. This work provides a promising strategy of designing bifunctional electrocatalysts for syngas generation with stable H 2 /CO ratio across a wide potential range.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
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2021
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IF 9.811
Xiangyang Yao,Kaihong Chen,Li-Qi Qiu,Zhi-Wen Yang,Liang-Nian He
Visible light-induced photocatalytic CO2 reduction reaction (CO2RR) is a feasible and promising option to tackle the greenhouse effect and energy crisis. Herein, two ferric porphyrin-based porous organic polymer semiconductors, hereafter referred to as POPn-Fe (porous organic polymers, n = 1 or 2, corresponding to a benzene/biphenyl unit as a linker between porphyrin units), are synthesized for the visible light-driven CO2RR to produce syngas. The CO/H2 evolution rates for POP2-Fe under irradiation >420 nm are found to successfully reach up to 3043 and 3753 μmol g–1 h–1, respectively. Interestingly, the experiment results imply that the ferric porphyrin site could be responsible for CO evolution and the uncoordinated porphyrin unit in POPn or POPn-Fe semiconductors may be obligate for H2 formation. Furthermore, as evidenced by Mott–Schottky plots, the extended π-conjugation with the biphenyl linker makes POP2-Fe a lower conduction band potential, which helps the ferric porphyrin sites capture electrons from the photosensitizer, thus producing more CO to realize selectivity control. Also, the efficient catalytic activity of POP2-Fe is presumably attributed to the accelerated charge transfer as well as facilitates photogenerated electron and hole separation. This work offers an elegant strategy to design and optimize earth-abundant metal visible light photocatalysis for CO2 reduction to syngas with CO/H2 ratio control.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF CATALYSIS
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2020
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IF 7.888
Lei Liu,Xiao-Chao Chen,Shu-Qing Yang,Yin-Qing Yao,Yong Lu,Ye Liu
Formic acid (FA) is one kind of important bulk chemicals, which is recognized as a sustainable and eco-friendly energy carrier to transport H 2 via dehydrogenation or CO via decarbonylation. Expectantly, FA upon decomposition into H 2 and CO could be used as the syngas alternative for hydroformylation. In this paper, the behaviors of FA to release H 2 as well as CO following the distinct pathways were carefully investigated for the first time, and then established a new hydroformylation protocol free of syngas. It was found that the atmospheric hydroformylation of olefins with formic acid (FA) as syngas alternative was smoothly fulfilled over Xantphos ( L1 ) modified Rh-catalyst under mild conditions (80 °C, Rh concentration 1 mol %, 14 h), resulting in >90% conversion of the olefins along with the high selectivity to the target aldehydes (>93%). By using FA as syngas source, the side-reaction of olefin-hydrogenation was greatly depressed. The in situ FT-IR and the high-pressure 1 H NMR spectroscopic analyses were applied to reveal how FA behaves dually as CO surrogate and hydrogen source over L1 -Rh(acac)(CO) 2 catalytic system, based on which the deeply insight into the catalytic mechanism of hydroformylation of olefins with FA as syngas alternative was offered.
研究领域:
催化化学
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绿色化学
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能源化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Chen Zeng,ZhiWei Jiang,Yongjian Zeng,Suyu Zhang,Rafael Luque,Kai Yan
H 2 -rich syngas production via microwave-assisted pyrolysis (MAP) of lignocellulosic biomass has recently gained significant attention in biorefineries. Herein, a novel pearl-like calcium oxide (P-CaO) was developed to investigate the dual roles of CaO in H 2 enhancement and CO 2 absorption during MAP of lignocellulosic biomass, dedicated to achieving high production of H 2 -rich syngas. Utilizing a self-constructed MAP system, the different catalytic performance between P-CaO and other metal oxides were examined, revealing that our P-CaO produced the highest H 2 yield (257 NmL/g corn stover , 7.6 times higher than no-catalyst group and 2.2 times higher than commercial CaO group), and lowest CO 2 production (44 NmL/g feedstock ), with syngas purity exceeding 72 vol% at 600°C. This increase in H 2 -rich syngas production demonstrated universal applicability across other biomass feedstocks. Finally, the study delved into the microstructural changes and phase transition mechanisms of P-CaO, shedding insights into gas formation pathways. The P-CaO nanoparticles, with abundant alkaline sites, excellent adsorption capacity and large specific surface area due to aggregate, facilitate the secondary cracking of organic intermediates like phenols, thus promoting the production of H 2 , while CO 2 adsorption derives a favorable shift in the water–gas shift equilibrium. These findings are expected to offer critical insights and serve as a reference for the development of efficient catalysts in the next-generation hydrogen industry.
研究领域:
能源科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）