SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Yu Fan,Bowen Lu,Ziqiang Han,Cong Luo,Liqi Zhang
CeO 2 support inhibits CaO sintering, and oxygen vacancy influences CO 2 hydrogenation performance, making CeO 2 widely applied in Integrated CO 2 capture and in-situ conversion technology for reverse water–gas shift (ICCC-RWGS). Oxygen vacancy concentration was dependent on the morphology of CeO 2 , which would affect metal dispersion and CO 2 hydrogenation conversion. However, Very little is known about the morphology effect of CeO 2 on the carbon capture and in-situ hydrogenation performance of DFMs. Here, Cu/CeO 2 with different CeO 2 morphologies was synthesized, and high Cu dispersion was achieved on Cu/CeO 2 -R, exhibiting the best CO 2 hydrogenation performance. Integrated Cu/CeO 2 with CaO by physical mixing method, CaO-Cu/CeO 2 was used to investigate the morphology effects of CeO 2 on the performance of CaO-Cu/CeO 2 for integrated CO 2 capture and conversion to CO. CaO-Cu/CeO 2 -R exhibited the best capture-hydrogenation performance (CO 2 conversion rate of 75 %, CO production rate of 9.72 mmol/g). The CeO 2 -R provided more surface oxygen vacancies, enhancing carbonate hydrogenation. The larger specific surface area and {1 1 0} crystal plane of CeO 2 -rod enhanced Cu dispersion, and the smaller particle size of CeO 2 -R enhanced its interaction with CaO, improving the cyclic stability of CaO-Cu/CeO 2 -R. The hydrogenation performance of CaO-Cu/CeO 2 was dependent on the morphology of CeO 2 , providing insights into the design of high-activity metal catalytic components in ICCC-RWGS.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Jun Zhang,Chengyu Li,Sheng Hu,Jing Gu,Haoran Yuan,Yong Chen
In the present study, CuO and Cu 2 O were employed in H-transfer transformation of bio-based furfural (FFR) using methanol as both the solvent and an in-situ hydrogen source , to clearly elucidate the catalytic mechanism of copper oxides (CuO x , x = 0.5, 1) during the reaction. A number of characterization techniques including XPS , H 2 -TPD, in-situ FTIR, etc., were undertaken to track the state of copper species. Owing to the synergistic effect of in-situ generated H 2 , Cu 0 species and CuO x derived Brønsted/Lewis acid sites, FFR could be efficiently hydrogenated into FA and subsequently deoxygenated into MF in methanol. The combined results from in-situ characterizations and experiments show that the FFR-to-FA (FA, furfuryl alcohol) and FFR-to-MF (MF, 2-methylfuran) conversions largely depended on the hydrogen production capability from methanol reforming and FFR adsorption strength over CuO x . Density functional theory (DFT) calculations demonstrated that the CuO(200) surface revealed lower free energy and energy barriers for methanol reforming and FFR transfer hydrogenation. This study provides a promising guidance for reasonably designing copper-based materials in the hydro-upgrading of bio-based unsaturated molecules into value-added chemicals in methanol without external H 2 supply.
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
JOURNAL OF THE ENERGY INSTITUTE
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2024
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IF 5.6
Shu-Ting Hu,Yue-Lun Wang,Qing-Gang Wang,Han-Bing Gao,Wen-Jie Gu,Wei-Hua Zhao,Yun-Peng Zhao,Jing-Pei Cao,Lin-Jun Zhu
The introduction of in situ hydrogen donors to obtain a high H/C eff ratio is an effective way to upgrade coal pyrolysis volatiles to light aromatics. In this study, the influence of different in-situ hydrogen suppliers in catalytic reforming of coal pyrolysis vapors was explored. The abilities of active hydrogen donation were greatly corresponded to structures of hydrogen donors. Isopropanol showed the best catalytic performance due to the release of a large amount of active α-H as a result of negative inductive effect of hydroxyl. Whereas tertbutanol showed the poorest catalytic performance owing to the lack of α-H. Meanwhile, the effect of in-situ hydrogen production via steam reforming with different alcohols on light aromatic yields was investigated. The highest BTEXN yield was obtained under in-situ hydrogen production from isopropanol steam reforming. Two circumstances of hydrogen supply were further compared. Relatively higher BTEXN yield was presented in the reaction of methanol steam reforming than that of using methanol solely. However, higher BTEXN yield was contrarily obtained from sole isopropanol as a hydrogen donor despite lower H 2 production was gained compared to the case of isopropanol steam reforming. The fact was probably ascribed that high electron-withdrawing effect of hydroxyl for isopropanol promoted the cleavage of α-C-H bond and favored the transfer of active hydrogen to reactants over acid sites.
研究领域:
化学工程
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能源科学
✓ 已验证
DOI
高影响因子
Journal of Environmental Chemical Engineering
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2024
·
IF 7.4
Yu Fan,Bowen Lu,Xinyu Zhi,Cong Luo,Liqi Zhang
NiFe 2 O 4 exhibits excellent redox properties and is widely applied in CaO-NiFe 2 O 4 chemical looping processes. However, rapid sintering of Ni-Fe alloy under reaction conditions limited its industrial applications. The CeO 2 -NiFe-CaO were synthesized through a physical mixing method with NiFe 2 O 4 as a precursor, and its CO 2 capture capacity and in-situ hydrogenation performance were conducted on ICCC-RWGS reaction under different conditions. 20CeO 2 -NiFe-CaO exhibited a CO yielding of 9.35 mmol/g at 650 °C. During the carbon capture stage, CO 2 was adsorbed by CaO, leading to the formation of CaCO 3 . In the hydrogenation conversion stage, hydroxyl groups were generated on the surface, combining with CaCO 3 to produce formate species, further generating H 2 O and CO. 15CNF-CaO exhibited superior cyclic ICCC-RWGS reaction performance compared to 15NF-CaO, with a CO yield of 1.88 mmol/g after 40 cycles. CeO 2 inhibited the sintering of catalytic components, preserving a higher specific surface area and smaller particle size. Furthermore, CeO 2 in 15CNF-CaO inhibited carbon deposition and enhanced in-situ hydrogenation performance, exhibiting better CaO regeneration capability and better cyclic stability. These results could provide insight for designing the DFMs for the ICCC-RWGS process.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Cleaner Production
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2018
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IF 5.651
Heng Zhong,Cailing Jiang,Xi Zhong,Jie Wang,Binbin Jin,Guodong Yao,Ligang Luo,Fangming Jin
Conversion of biomass and waste oils to alkanes for the production of aviation fuel is attracting increasing research interests since it can provide sustainable energies from renewable resources to substitute the fossil fuels. In this process, the deoxygenation of fatty acids to alkanes is the key reaction. However, previous methods of fatty acids deoxygenation require gaseous hydrogen, noble metal catalyst and/or organic solvent, which are adverse to the sustainable development. In this work, a novel and simple method of deoxygenation of fatty acids to alkanes is proposed by using a commercial nickel (Ni) powder as the catalyst without any pre-treatment and water as both environmental-friendly solvent and sustainable hydrogen source . The hydrogen in situ generated from water exhibited a much higher activity than gaseous hydrogen for the deoxygenation of fatty acids, and an alkane yield of 90% was successfully achieved. The Ni catalyst is stable and still maintains high activity after recycles. This proposed process is simple, economical, sustainable and environmental-friendly, thus is promising for the practical application.
研究领域:
可再生资源
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催化化学
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能源转化
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2021
·
IF 7.92
Xixi Liu,Yanxin Wang,Bo Li,Bing Liu,Wei Wang,Nian Xiang,Zehui Zhang
The catalytic acceptorless dehydrogenation of primary amines into imines and H 2 represents one of the most important organic transformations, and the in-situ utilization of the generated H 2 for chemical reduction reactions has never been reported in previous research. Herein, nitrogen-doped carbon supported nickel catalysts (abbreviated as Ni/NC-T, where T represents the pyrolysis temperature) were facilely prepared by the simple pyrolysis process, and the Ni/NC-600 catalyst demonstrated excellent catalytic performance towards the tandem reaction of the dehydrogenation of primary amines into imines and the subsequent hydrodeoxygenation of sulfoxides into sulfides using the in-situ released H 2 , affording high to quantitative yields. The developed methods demonstrated some advantages such as the use of heterogeneous non-noble metal catalysts with low cost and high stability, and the in-situ utilization of generated H 2 with high atom efficiency.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
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2020
·Vol. 10
·期 12
·1379
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IF 3.52
He Liu,Shiguang Fan,Xu Gong,Jian Wang,Aijun Guo,Kun Chen,Zongxian Wang
Partial hydrogenation of anthracene under CO-H2O, N2-H2O, and H2-H2O over Fe-based catalysts was studied at 400 °C and 10 MPa. Results show that the Fe-based catalysts display obvious catalytic activity for anthracene hydrogenation under CO-H2O instead of hydrogenation under N2-H2O and H2-H2O. The activity follows in the order of Fe(NO3)3·9H2O > Fe naphthenate > FeSO4·7H2O. Even though the amount of molecular hydrogen remains higher than that of in situ hydrogen, the anthracene conversion with in situ hydrogen is remarkably higher. It demonstrates that the in situ hydrogen is more active than molecular hydrogen for PAH hydrogenation. To further reveal the exact fate of these Fe-based catalysts, the decomposed products under CO-H2O, N2-H2O and H2-H2O were characterized by TG, XRD, and TEM. Results indicate that the Fe3O4species play a key role in hydrogenation of anthracene under CO and H2O. Higher catalytic activity for Fe(NO3)3·9H2O is due to its complete decomposition at 350 °C to acquire higher concentration of active Fe3O4species. The possible form of in situ hydrogen during this process is also discussed. Given that heavy oil contains abundant polyaromatics, these results are meaningful for enhancing hydrogen shuttling to heavy oil by producing natural hydrogen donors and, thus, benefiting the high-efficient upgrading.Keywords:PAH hydrogenation;in situ hydrogen;water gas shift reaction;natural hydrogen donors
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
Catalysts
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2019
·Vol. 9
·期 11
·952
·
IF 3.444
Huiyuan Xue,Jingjing Xu,Xingxing Gong,Rongrong Hu
The in-situ hydrodeoxygenation of bio-derived phenol is an attractive routine for upgrading bio-oils. Herein, an active trimetallic Ni-Cu-Co/Al2O3catalyst was prepared and applied in the in-situ hydrodeoxygenation of bio-derived phenol. Comparison with the monometallic Ni/Al2O3catalyst and the bimetallic Ni-Co/Al2O3and Ni-Cu/Al2O3catalysts, the Ni-Cu-Co/Al2O3catalyst exhibited the highest catalytic activity because of the formation of Ni-Cu-Co alloy on the catalyst characterized by using X-ray powder diffraction (XRD), temperature programmed reduction (TPR), N2physisorption, scanning electron microscope (SEM), and transmission electron microscope (TEM). The phenol conversion of 100% and the cyclohexane yield of 98.3% could be achieved in the in-situ hydrodeoxygenation of phenol at 240 °C and 4 MPa N2for 6 h. The synergistic effects of Ni with Cu and Co of the trimetallic Ni-Cu-Co/Al2O3catalyst played a significant role in the in-situ hydrodeoxygenation process of phenol, which not only had a positive effect on the production of hydrogen but also owned an excellent hydrogenolysis activity to accelerate the conversion of cyclohexanol to cyclohexane. Furthermore, the catalyst also exhibited excellent recyclability and good potential for the upgrading of bio-oils.Keywords:bio-derived phenol;Ni-Cu-Co/Al2O3;in-situ hydrodeoxygenation;cyclohexane;hydrogenolysis
研究领域:
催化化学
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
Carbon Capture Science & Technology
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2024
·
IF 10.4
Daocheng Liu,Liangyong Chen
The impacts of steam on hydrogenation of dual function materials (DFM) for Integrated CO 2 Capture and in-situ methanation (ICCM) is a new area requiring detailed investigations prior to industrialization. This work investigated impacts from steams on hydrogenation of Ru-Na 2 CO 3 /γ-Al 2 O 3 DFM for ICCM that containing Na 2 O adsorbent, Ru sites, and γ-Al 2 O 3 support. DFM performance was examined in cyclic reactions as introducing external steam during hydrogenation, and the behaviors of adsorbed CO 2 species during hydrogenation were characterized by in-situ DRIFTS and H 2 -TPSR. CH₄ selectivity decreased sharply from 84.3 % to 1.2 % as increasing external steam concentrations to 20 vol.%, and the conversion of adsorbent component decreased from 298.5 μmol g -1 to 167.1 μmol g -1 . b -CO 3 2- and m -CO 3 2- formed at Na 2 CO 3 /γ-Al 2 O 3 interface were the carbonate species that could be hydrogenated into CH 4 , some of which were desorbed into CO 2 due to moisture-driven desorption effects. With the presence of external steam in H 2 reactants, the conversion of carbonate species is a competing process between hydrogenation and moisture-driven desorption. In ICCM reaction with external steam present, b -CO 3 2- was preferred to be desorbed into CO 2 ; while for m -CO 3 2- , desorption into CO 2 by steam and hydrogenation into CH 4 proceeded in parallel. Strong moisture-driven desorption effects from steam product were demonstrated in a fixed-bed reactor, which also led to rapid decrease of localized selectivity of CH 4 along bed height.
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Zihao Zhang,Siyu Yao,Changxue Wang,Miaomiao Liu,Feng Zhang,Xiaobing Hu,Hao Chen,Xin Gou,Kequan Chen,Yimei Zhu,Xiuyang Lu,Pingkai Ouyang,Jie Fu
Catalytic in situ hydrogenation of 5-hydroxymethylfurfural (5-HMF) to 2,5-dimethylfuran (DMF) has received a great interest in recent years. However, the issue of the consumption of expensive hydrogen donors, such as secondary alcohols, limits its applications. In this work, a ternary CuZnCoO x catalyst, exhibiting a 99% yield of DMF from in situ hydrogenation of 5-HMF with ethanol as economical hydrogen donor, is developed. High resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR) reveal the synergy effect of each components. Reaction mechanism studies unravel the CoO x results in promoting in situ H 2 production from ethanol, the zinc oxide accelerates the aldehyde group ( CHO) hydrogenation to hydroxymethyl group ( CH 2 OH) and the formation of Cu-Co alloy significantly facilitate the hydrogenation of 5-HMF. Additionally, this ternary CuZnCoO x catalyst exhibits superior recyclability without losing any activity during 6 cycles experiment.
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
ACS Applied Materials & Interfaces
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2018
·
IF 8.097
Yanzi Wang,Yongzhen Chen,Caihong Wang,Jing Sun,Zhiping Zhao,Wenfang Liu
Enzymatic CO2 reduction can provide value-added chemicals from greenhouse gases at ambient temperature and pressure. However, poor solubility of CO2 results in a low conversion rate. In this work, polyethylenimine (PEI) was attached onto the surface of poly(acrylic acid)-grafted (PAA-grafted) polyethylene membranes, and then, the membranes were used in an integrated process of CO2 capture and in situ hydrogenation. Modification conditions were optimized with a surface amino group density of PEI-modified membranes as the characteristic parameter, and then, SEM, FTIR, and XPS analyses were conducted. The effect of PEI-modified membranes on enzyme-catalyzed CO2 conversion to formic acid, regeneration conditions, and reusability were studied. The results show that when the grafting ratio of PAA increased, surface amino group density of PEI-modified membranes increased up to 6.00 × 10–7 mol/cm2 and then kept constant. The optimum modification time, temperature, and PEI concentration were 40 min, 40 °C, and 0.3 wt %. With the same concentration, PEI-1800 could bring more amino groups than PEI-600. SEM, FTIR, and XPS results further confirmed PEI attachment. Introduction of membrane-supported PEI with 5.86 × 10–6 mol of amino groups facilitated greatly enzymatic CO2 hydrogenation, and the initial reaction rate increased from 0.280 to 6.90 μM/min. After being regenerated in ammonia, PEI-modified membranes could be reused, and the relative reaction rate was, respectively, 88.0% and 65.7% after 5 and 10 cycles.
研究领域:
化学工程
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环境科学
·
生物技术
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Xianwen Zhang,Ping Li,Bin Xu,Jingxia Wang,Guangyin Fan,Xiaobin Zhang,Xiaoqiang Liu,Kaiming Zhang,Weidong Jiang
Selective hydrogenation of halogenated nitrobenzenes (XNBs) to halogenated amines (XANs) is of great importance for practical applications. Non-noble metal-based catalysts have shown prominent advantages in price and reserves accompanying low activity and selectivity toward the hydrogenation of halogenated nitrobenzenes (XNBs) even under harsh conditions. In this work, inexpensive Ni–Co-based composites (NxCC) were prepared for in situ tandem hydrogenation of XNBs to XANs by using hydrogen released from ammonia borane (AB) hydrolysis under ambient pressure. The results show these NxCC samples exhibited superior catalytic performance against Co3O4 or NiO samples. A selected N0.2CC catalyst as the mainly screened one can quantitatively convert XNBs to XANs with unprecedented activity with 100% XAN conversion. This catalyst can completely convert m-chloronitrobenzene (m-CNB) to m-chloroaniline (m-CAN), suggesting N0.2CC efficiently suppresses the further dichlorination of m-CAN. Recycling test shows the N0.2CC possesses higher stability and recyclability. The N0.2CC catalyst was found to be a dual catalyst that synergistically catalyzes both the AB dehydrogenation (about 1735 mL min–1 g–1 of hydrogen generation rate) and the subsequent hydrogenation (almost 100% conversion) of XNBs. Notably, it is the first time that the rapid in situ hydrogen activation (IHA) which facilely arouses the efficient hydrogenation of adsorbed substrate on the surface of catalyst has been elaborated. From a unique perspective, distinctive and simple control experiments were innovatively designed for testifying the advantage of tandem hydrogenation in contrast with traditional hydrogenation. This work presents an efficient and environmental strategy to selectively produce XANs from XNBs using high-performance non-noble metal composites.
研究领域:
化学
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催化科学
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环境科学
✓ 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）