ENVIRONMENTAL POLLUTION
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2022
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IF 9.988
Zhigang Zhao,Zheng Li,Xiangkun Zhang,Tan Li,Yuqing Li,Xingkun Chen,Kaige Wang
The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO 2 catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate . As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C 4 –C 22 . The gas products are primarily CH 4 along with a small amount of C 2 H 6 and C 3 H 8 . High yield of CH 4 as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.
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
PubMed
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
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产品关联
DOI
高影响因子
ACS Catalysis
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2023
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IF 12.9
Chao Zhang,Yingqiang Li,Yue Xie,Zhanjiang Yu,Xin Wan,Xinzhi Wang,Jiaan He,Junlang Li,Zhenguo Chen,Xiaoyong Li,Xiaohui Yi,Zhaoli Wang,Guang-Guo Ying,Dionysios D. Dionysiou,Mingzhi Huang
Selective hydrodehalogenation and hydrodearomatization of toxic chlorophenols into value-added chemicals represents a grand challenge for their efficient reutilization. For this purpose, single-atom catalysts (SACs) could be a strategy with relatively high catalytic selectivity and atom utilization but suffer from the catalytic limitation caused by low metal loading densities. Graphdiyne and γ-graphyne are considered promising substrates of SACs with excellent catalytic properties. Additionally, their quantum dots with nanometer size are expected to supply numerous surface anchoring sites and large atom spacing to confine metal cations to synthesize high-loading SACs. Here we report a synthesis approach for high-loading Ru SACs anchored on graphdiyne/γ-graphyne quantum dots (GDQD-Ru/GNQD-Ru), which exhibit remarkably higher turnover frequency (TOF) and selectivity (>99%) of hydrodehalogenation and hydrodearomatization of chlorophenols than graphdiyne/γ-graphyne nanosheet-based Ru SACs and nanoparticles. There is no significant selectivity decrease in chlorophenol transformation by GDQD-Ru/GNQD-Ru observed in 5 catalyst reuse cycles. GDQD-Ru/GNQD-Ru contribute to nearly exclusive hydrodehalogenation and hydrodearomatization without altering any other bonds in chlorophenols. Experimental results and theoretical calculations reveal that GDQD-Ru is more prone to lower energies of rate-limiting steps in H2-driven chlorophenol transformation than GNQD-Ru. The results confirm that graphdiyne/γ-graphyne quantum dots play crucial roles in facilitating the metal atom loading of SACs. Ru loadings are 27.6 and 16.0 wt % in GDQD-Ru/GNQD-Ru, approximately 7-fold and 4-fold higher than reported Ru SACs, respectively. This study provides mechanistic insights toward the roles of high-loading Ru SACs on sp- and sp2-hybridized carbonaceous substrates in selective hydrodehalogenation and hydrodearomatization.
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
FUEL
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2022
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IF 8.035
Xiaoxian Li,Min Lin,Rui Li,Qiang Lu,Mingde Yang,Yulong Wu
In this work, methods employing ethanol for dispersion as well as precursor combination by rotary evaporation were combined to produce Ni-based ZSM-22 catalysts. The catalytic activity in palmitic acid deoxygenation over Ni/Z22@E was enhanced compared with that of the wet-impregnated method. The conversion of palmitic acid reached 98.9 %, in which C16/C15 alkane was as high as 4.07. The Ni species on the surface of catalysts showed strong stability so that not susceptible to inactivation by coking or leaching. In addition, the mechanism and kinetics of the palmitic acid deoxygenation reaction were analyzed. The results showed that the ethanol dehydration reaction was the most difficult to occur, and the high C 16 alkanes selectivity can be attributed to the low activation energy of the hydrodeoxygenation (HDO) pathway. Both experimental and kinetics calculation results suggested that there may be a mechanistic change in the fatty acid deoxygenation reaction at around 240 °C that resulted in a large increase in the hydrodecarboxylation (HDX) pathway. Based on this, selected adjustments of the products were proposed for fatty alcohols below 220 °C, C 16 alkanes between 260 and 280 °C, and C 15 alkanes above 280 °C.
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
ACS Sustainable Chemistry & Engineering
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2022
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IF 9.224
Ruixue Liu,Xinli Li,Zhendi Jia,Yiyun Wang,Yanli Peng,Congming Tang,Zhi Chen,Lin Dong
The hydrodeoxygenation of lactic acid (LA) to propionic acid (PA) is of great significance for the conversion of biomass to valuable products; however, it remains a great challenge because of the trade-off between LA conversion and PA selectivity. Here, we prepared ultrathin MoS2 nanosheets containing rich sulfur vacancies by lithium exfoliation. With the increase of the lithium exfoliation time, sulfur vacancy in MoS2 is accordingly increased and LA adsorption and activation on sulfur vacancy is enhanced. Increasing sulfur vacancy lowered the valence band simultaneously and enhanced the dissociation of the H2 molecule. Density functional theory (DFT) calculations showed that the sulfur vacancy efficiently adsorbed α-C–OH of the LA molecule, weakened the C–O bond, and achieved selective conversion of LA to PA. At 215 °C, 92.4% of LA conversion and 95.8% PA selectivity were achieved over the sulfur vacancy-rich MoS2 nanosheets, which broke the activity–selectivity trade-off on hydrodeoxygenation of LA, and notably surpassed those of previously reported catalysts. More importantly, the activity of the catalyst remained almost unchanged after 8 cycles of reaction.
研究领域:
催化化学
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生物质转化
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材料科学
✓ 已验证
DOI
高影响因子
RENEWABLE ENERGY
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2022
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IF 8.634
Siteng Rong,Hongzi Tan,Zhaobin Pang,Zhiyuan Zong,Rongrong Zhao,Zhihe Li,Zhe-Ning Chen,Ning-Ning Zhang,Weiming Yi,Hongyou Cui
Lignin could be depolymerized into large amount of phenolic compounds via fast pyrolysis . The upgrade of phenolic compounds via hydrodeoxygenation (HDO) involves multiple reaction pathways. It is challenging to selectively remove the oxygen-containing groups while keeping the aromatic rings intact. In this work, hierarchical Nb 2 O 5 (H–Nb 2 O 5 ) microspheres with abundant oxygen vacancies were synthesized to anchor the Pd clusters, which is featured with strong metal-support interaction via the electron transfer between Pd species and Nb species. For phenol HDO reaction, the oxygen vacancies were prone to interact with the phenolic hydroxy groups, resulting in phenol molecule adsorbed in a “nonplanar” manner, greatly weakening the C Ar -O bonds and averting the ring hydrogenation. Besides, the activated hydrogen atoms on Pd clusters could migrate to the vicinity of oxygen vacancies via spillover, promoting the cleavage of C Ar -O bond to obtain benzene. Current work provides a deep insight into the synergetic catalytic mechanism of Pd/H–Nb 2 O 5 catalyst for phenol HDO reaction, and also sheds light on the design and synthesis of high-efficient catalysts in other heterogeneous catalysis fields.
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 PROCESSING TECHNOLOGY
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2022
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IF 8.129
Huiyuan Wang,Tan Li,Jing Su,Kai Miao,Kaige Wang
Lignin hydropyrolysis was investigated in a high-pressure micro-reactor with on-line analysis characterization of products. The influences of atmosphere, pressure, and temperature on product formation during lignin pyrolysis were quantitatively discussed. The presence of hydrogen, elevated pressure and temperature favored the production of condensable vapors and permanent gas while inhibited the formation of char. High-pressure hydrogen boosted the conversion of methoxy phenolics to non-methoxy phenolics, and facilitated the generation of hydrocarbon condensable vapors and hydrocarbon gases. Non-methoxy phenolics were major condensable vapor from lignin hydropyrolysis. Yield of non-methoxy phenolics reached 19.68C% at 3 MPa and 500 °C. The monocyclic and polycyclic aromatic hydrocarbons as well as condensable aliphatic hydrocarbons were observed from lignin hydropyrolysis. Methane was the most abundant gas product from lignin hydropyrolysis, yield of which was 10.27C% at 2 MPa and 600 °C. The formation mechanisms of typical products were proposed and verified with experiments using model compounds. The formation of non-methoxy phenolics, monocyclic aromatic hydrocarbons and aliphatic hydrocarbons is related to the substitution of methoxy (and its methyls) and phenolic hydroxyl groups on benzene rings by alkyls, alkenyls and hydrogen radicals, as well as the hydrogenation of π bonds .
研究领域:
化学工程
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
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2022
·Vol. 12
·期 11
·1328
·
IF 4.501
Liang-Qiu Huang,Zhi-Jun Diao,Bo Chen,Qing-Pan Du,Kai-Yang Duan,Si-Jia Zhao
Efficient depolymerization of C–O linkages is essential for converting lignin into fuels and higher value-added chemicals. In this work, CoRuP/SiO2, an amorphous Ru-Co phosphide composite, was fabricated for the efficient hydrogenolysis of ether linkages. The 4–O–5 andα–O–4 linkages containing lignin-related compounds, such as diphenyl ether, benzyl phenyl ether, 3-methyl diphenyl ether, and dibenzyl ether, are selected as representatives of linkages in lignin. Under mild conditions, Ru-containing metallic phosphides have high-performance for the catalytic depolymerization of C–O linkages. Compared with other catalysts, CoRuP/SiO2shows an outstanding selectivity for benzene and excellent efficiency in depolymerizing diphenyl ethers, yielding only a small amount of by-products. Furthermore, the total acidity shows a linear relationship with the hydrogenolysis reactivity in cleaving aromatic ether bonds. The mechanisms for the catalytic hydrogenolysis of 4–O–5 andα–O–4 bonds over CoRuP/SiO2are proposed. Moreover, two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance spectroscopic analysis demonstrates that CoRuP/SiO2could effectively depolymerize C–O bonds of lignin. These dominant hydrogenolysis products from lignin have excellent potential in the production of high value-added drugs or pharmaceutical intermediates. The hydrogenolysis of lignin can be a highly efficient alternative to the existing method of lignin utilization.Keywords:hydrogenolysis;C–O linkages;metallic phosphides;reaction pathway
研究领域:
化学工程
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可再生能源
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2020
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IF 3.573
Bowen Luo,Rongxuan Li,Riyang Shu,Chao Wang,Jingtao Zhang,Ying Chen
Simple and efficient catalytic routes have been explored to upgrade the raw lignin oil. Though homogeneous catalysis is easy to operate and possesses a high reaction rate, it also suffers from the difficulty of product separation. In this work, we used H3BO3 as a novel homogeneous catalyst coupled with Ru/C to overcome the separation problem and carry out the hydrodeoxygenation (HDO) of phenolic compounds and raw lignin oil. H3BO3 showed an outstanding performance over the liquid organic and mineral acids, with a good catalyst recyclability. Phenolic model compounds including monomers and dimers can be efficiently converted into cycloalkanes with yields close to 100%. Moreover, the raw lignin oil also had a good HDO result by using this bifunctional catalyst (H3BO3 and Ru/C). The content of hydrocarbons increased from 7.9% to 93.1% at 260 °C, which promoted the upgraded lignin oil capable to be used as fuel directly.
研究领域:
化学工程
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可再生能源
✓ 已验证
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Jie Wang,Quanxing Zheng,Hongliang Lu,Jianqiang Fan,Xiaohua Deng,Wenjing Song,Pengfei Ma,Weikun Lai
Selective aqueous hydrogenolysis of cellulose to valuable ketones and alcohols is attractive for biomass utilization. This work developed a TiO 2 layer coated MoO 3 nanorod supported Ni catalyst for the hydrogenolysis of cellulose to ketones and alcohols, which achieved a maximum hexacarbon keto-alcohols yield of 71.2 % with a complete cellulose conversion at 220 °C and 3 MPa H 2 . The interaction of Ni and TiO 2 -MoO 3 oxides provided effective channels for hydrogen transfer, thereby boosting the reduction of MoO 3 to form MoO 2 species. More Lewis acid sites were created which facilitated the isomerization of glucose and retro -aldol condensation of fructose. The cleavage of C O bonds in hydroxyl-containing intermediates thus promoted their selective hydrogenolysis to form ketones and alcohols. Particularly, Ni TiO 2 /MoO 3 catalyst demonstrated excellent reusability due to the protective coating of TiO 2 layer and could be widely used in selective hydrogenolysis of various oxygen containing compounds.
研究领域:
化学工程
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可再生能源
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2018
·Vol. 124
·期 2
·683-699
·
IF 1.515
Zhu Min,Chen Changlin
A series of Pt–yLi 2 B 4 O 7 /WO x /ZrO 2 (y = 0, 0.5, 1, 2 wt%) catalysts were prepared by varying the content of Li 2 B 4 O 7 through the method of coimpregnation-calcination. The obtained catalysts were used for the selective hydrogenolysis of glycerol to 1,3-propanediol. Meanwhile, these catalysts were characterized by N 2 adsorption and desorption (BET), CO chemisorption, X-ray diffraction (XRD), NH 3 -temperature programmed desorption (NH 3 -TPD), H 2 -temperature programmed reduction (H 2 -TPR), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results showed that Pt–1Li 2 B 4 O 7 /WO x /ZrO 2 achieved the highest activity with glycerol conversion of 90.7% at 150 °C and 4 MPa and exhibited excellent stability over 200 h. Pt/WO x /ZrO 2 catalyst modified with Li 2 B 4 O 7 was able to enhance catalytic activity and stability, since Li 2 B 4 O 7 promoted the dispersion of Pt, increased the acid amount of the catalyst and strengthened the interaction between active components and support.
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
ORGANIC PROCESS RESEARCH & DEVELOPMENT
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2014
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IF 2.549
Kai Dong,Cheng H. Sun,Jian W. Song,Gai X. Wei,Si P. Pang
Synthesis of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane (TAIW) by catalytic hydrogenolysis of 2,6,8,12-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexaazaisowurtzitane (TADBIW), a key step for the synthesis of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW), has been first implemented under continuous flow conditions using the commercially available H-Cube Pro reactor. Several variables (i.e., reaction temperature, flow rate, and pressure) and the stability of the system have been investigated to optimize the operating conditions. The results show that a continuous flow system provides a better yield than a batch system. For instance, the yield is 99% at the optimized conditions, while the best yield from batch reactions is 92%. Continuous flow synthesis of TAIW has potential applications in improving the production technologies of HNIW for its many advantages over batch reactions.
研究领域:
化学合成
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材料科学
✓ 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）