JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2024
·Vol. 99
·期 4
·922-930
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IF 2.8
Dingshuo Zhang,Heqian Zhang,Yue Li,Daolai Sun,Jianhua Lv
BACKGROUND Levulinic acid is an important platform chemical derivable from lignocellulosic biomass. In this work, the hydrogenolysis of levulinic acid to produce 1,4-pentanediol was performed over some Co-based non-noble catalysts. The relationship between the catalyst properties and the catalytic activity was investigated, and the effects of the reaction conditions on the catalytic activity were studied. RESULTS The Co/ZrO 2 catalyst prepared by a coprecipitation method showed a high catalytic performance in the hydrogenolysis of levulinic acid to form 1,4-pentanediol. The calcination of Co/ZrO 2 significantly affected the catalytic activity, and a high calcination temperature of 750 °C could promote the formation of 1,4-pentanediol. Meanwhile, the reduction of Co/ZrO 2 at 400 °C in an H 2 flow was beneficial for producing 1,4-pentanediol, and the Co species after the reduction existed as the forms of Co 2+ and Co 0 . A high H 2 pressure and a moderate reaction temperature of 200 °C were beneficial for producing 1,4-pentanediol, and a high 1,4-pentanediol selectivity of 85.6% with a complete conversion of levulinic acid was obtained over the Co/ZrO 2 catalyst at 200 °C under an H 2 pressure of 7 MPa. CONCLUSION The Co species in the 400 °C-reduced Co/ZrO 2 catalyst existed as the forms of Co 2+ and Co 0 . It was proposed that the synergistic effect of Co 2+ and Co 0 contributed to the effective formation of 1,4-pentanediol from levulinic acid. © 2024 Society of Chemical Industry (SCI).
研究领域:
化学工程
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可再生能源
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产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2021
·Vol. 151
·期 9
·2513-2526
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IF 3.186
Cui Kai,Qian Wei,Shao Zhengjiang,Zhao Xiuge,Gong Honghui,Wei Xinjia,Wang Jiajia,Chen Manyu,Cao Xiaoming,Hou Zhenshan
Furfural (FFR) is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Herein, we demonstrate that Ru nanoparticles (Ru NPs)-supported on a sulfonated carbon layer coated SBA-15 can be employed as an efficient bi-functional catalyst for one step conversion of FFR into 1,4-pentanediol (1,4-PeDO). The optimum bi-functional catalyst can afford the full the conversion of FFR and 86% selectivity to 1,4-PeDO. The catalysts have been characterized thoroughly by using a complementary combination of powder X-ray diffraction, N 2 adsorption–desorption, scanning/transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. The characterization revealed that acidic groups (–SO 3 H) have been introduced on the surface of the carbon layer coated SBA-15 support after sulfonation with 98% H 2 SO 4 and the surface acidity can be tuned facilely by the sulfonating time. Meantime, Ru(0) sites was highly dispersed via an impregnation and sequential reduction and directly adjacent to the surface –SO 3 H group. There existed an electronic interaction between Ru(0) sites and sulfonic groups, in which the electronic transfer from sulfonic sites to Ru(0) sites occurred. Brönsted acid sites (–SO 3 H) have a significant influence on the FFR conversion and the selectivity to 1,4-PeDO. The ordered mesoporous structure, the appropriate density of acid sites and the electron-rich Ru(0) sites accounted for the the excellent performance of the catalyst for an efficient production of 1,4-PeDO from FFR. Graphic Abstract
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
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产品关联
DOI
高影响因子
CHEMISTRY LETTERS
·
2022
·Vol. 51
·期 4
·395-398
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IF 1.715
Zhu Yue,Li Yue,Zhao Shipeng,Jing Ran,Zhang Heqian,Sun Daolai,Sato Satoshi
Hydrogenation of γ-valerolactone (GVL) to form 1,4-pentanediol (1,4-PDO) was performed over Co/ZrO2 catalysts with a Co metal loading of 15 wt. %. The calcination of Co/ZrO2 at high temperatures significantly promoted the catalytic activity irrespective of the decrease in the specific surface area. The 750 °C-calcined Co/ZrO2 with Co2+ species exhibited a high catalytic performance: a GVL conversion of 86.1% with a 1,4-PDO selectivity of 97.2% was achieved at 165 °C under 5 MPa H2 pressure.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2020
·Vol. 10
·期 13
·4412-4423
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IF 5.721
Qiang Liu,Zhenbo Zhao,Masahiko Arai,Chao Zhang,Ke Liu,Ruhui Shi,Peixuan Wu,Zhuangqing Wang,Weiwei Lin,Haiyang Cheng,Fengyu Zhao
The transformation of γ-valerolactone (GVL) into 1,4-pentanediol (1,4-PDO) and 2-methyltetra-hydrofuran (2-MTHF) in the presence of H2, one of the useful biomass conversion and utilization processes, was investigated with monometallic Cu/Al2O3 and bimetallic ZnCu/Al2O3 catalysts. A 10 wt% Cu-loaded monometallic catalyst produced 1,4-PDO and 2-MTHF in comparable quantities at a medium conversion (∼50%). When Zn was added in a range of Zn/Cu molar ratios of up to 2, in contrast, the catalysts yielded 1,4-PDO in a high selectivity of about 97% at low and high conversion levels. In addition, the 1,4-PDO selectivity over the ZnCu/Al2O3 catalysts remained almost unchanged during recycled runs. That is, the addition of Zn to Cu/Al2O3 switched the product selectivity and improved the catalyst stability and reusability. Furthermore, the physicochemical properties of the catalysts were characterized by several methods including XRD, TEM, TPR, XPS, FTIR of adsorbed pyridine, and so on. On the basis of those results, the relationships between the catalytic performance (activity, selectivity, and reusability) and the catalyst structural features were discussed.
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
Materials Today Sustainability
·
2023
·
IF 7.8
B. Putrakumar,Prem Kumar Seelam,G.S. Rao,N. Pethan Rajan,P. Bhanuchander,G. Raveendra,P. Vijayanand,U. Lassi,E.M. Bakhsh,S.B. Khan,S. Kim
This research work introduces highly dispersed Cu nanoparticles encapsulated into a nanoporous carbon (Cu@C) structure as an efficient catalytic system in selective hydrogenation of γ-valerolactone (GVL) to 1,4-pentanediol. The nanoporous carbon support and the catalysts were synthesized by sequential novel methods and characterized extensively by using a combination of different analytical techniques to determine the phase, textural, morphology, nanoparticles size, and distribution analysis, and redox behavior. The designed Cu@C embedded catalysts show moderately high activity in GVL hydrogenation with different Cu loadings. The effect of copper loadings was found to be a significant parameter in gaining the best performance in GVL conversion. The copper nanoparticles were uniformly distributed over the nano-scaled carbon structure with active metallic Cu(111) sites with high dispersion and promote GVL hydrogenation, efficiently. Over a 5Cu@C catalyst exhibited the highest GVL conversion (∼91%) and 1,4-pentanediol selectivity (∼97%) at 200 °C for a 5 h reaction time under a 5 MPa H 2 pressure. The dispersion of the active copper phase in combination with a smaller particle size and surface acidity is directly correlated with the catalytic performance activity. The effects of reaction parameters such as the reaction time, temperature, and H 2 pressure were systematically investigated. Overall, Cu@C is a promising non-noble metal-based catalytic system for the upgradation of biomass-based platform molecules via selective hydrogenation.
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
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
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2024
·
IF 6.3
Rui Kang,Dayi Guo,Xinyi Luo,Hui Pan
Catalytic hydrogenation of ethyl levulinate (EL) to 1,4-pentanediol (1, 4-PDO) could provide a potential approach to obtain valuable chemicals from renewable biomass. In this study, a CuZr/CoOx catalyst was developed based on a structural topotactic transformation process of layered double hydroxides. The prepared CuZr/CoOx catalysts possess a double functionality of metal-acid sites and showed superior catalytic activity in the production of 1, 4-PDO from cascade conversion of EL. A complete EL conversion (100 %) and 93.1 % 1, 4-PDO yield were obtained under optimized conditions over catalyst CuZr/CoOx-400. The co-existence of Cu 0 and Cu + on the surface of catalyst CuZr/CoOx was confirmed by XRD and XAES characterizations. In addition, the XPS results suggested a strong interaction between Co and Cu, which would effectively stabilize the Cu + species in the catalyst. The Cu 0 was believed to activate hydrogen, while the Cu + could promote the adsorption of carbonyl group of the substrate thus facilitating the hydrogenolysis. The introducing of Zr in the catalyst greatly improved the dispersion of Cu species and increased the abundance of the acid sites as revealed by the TEM and NH 3 -TPD analysis. Catalyst CuZr/CoOx-400 also exhibited highly catalytic activity after five reaction cycles. Together with the low cost of the non-precious metals, the CuZr/CoOx catalysts demonstrate a potential for the scaled-up application in the biomass refinery process.
研究领域:
催化化学
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生物质能
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可再生资源
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2019
·Vol. 21
·期 16
·4499-4511
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IF 9.405
Yuewen Shao,Kai Sun,Qingyin Li,Qianhe Liu,Shu Zhang,Qing Liu,Guangzhi Hu,Xun Hu
γ-Valerolactone (GVL) and 1,4-pentanediol (1,4-PDO) are value-added chemicals that can be produced from levulinic acid/ester via hydrogenation coupled with acid/base-catalyzed reactions. In this study, we demonstrate that the Cu-based catalysts produced via the hydrotalcite precursors with tunable distribution of acidic and basic sites could, according to the requirement of the target products, effectively tune the production of GVL or to 1,4-PDO from levulinic acid/ester. The abundant Brønsted acid sites over the CuAl catalyst suppressed the opening of the ring of GVL, achieving a higher GVL selectivity while inhibiting 1,4-PDO formation. The introduction of Mg species to the catalyst significantly increased the abundance of the basic sites on the surface of the catalyst, which was essential for the selective conversion of GVL to 1,4-PDO via the opening of the ring structure of GVL, the rate-determining step in the conversion from levulinic acid/ester to 1,4-PDO. In addition, the CuMgAl catalyst showed a much superior catalytic stability to the CuMg or CuAl catalyst due to the more stable crystal structure, the more developed porous structure, the higher dispersion of the Cu species and the higher capability to suppress the growth of metallic Cu species under hydrothermal conditions.
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
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2023
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IF 4.2
Dongying Yan,Ruilin Feng,Yanlong Qi,Chenxi Bai
Selective synthesis of 1,3-pentadiene without 1,4-pentadiene formation is challenging as well as rewarding because of the widespread use of 1,3-pentadiene in adhesive, paint, and curing agent production. Herein, modified K–Ce/ZrSi catalysts with acid–base sites were synthesized for the production of 1,3-pentadiene from 1,4-pentanediol. The overall 1,3-pentadiene yield was 74.7%, while the 1,4-pentadiene yield was 1.3%. On the catalyst, two parallel routes (direct dehydration and dehydra-decyclization) for the conversion of 1,4-pentanediol to 1,3-pentadiene were disclosed. The 4-position hydroxyl group was first activated and then eliminated on the acid sites. It was considered that the acid–base sites of catalysts exhibited a synergistic effect for the selective dehydration of 1,4-pentanediol to 1,3-pentadiene, where the medium strength Lewis acid sites and weak base sites were responsible for the elimination of the hydroxyl group and the corresponding β1-H, thereby inhibiting the formation of 1,4-pentadiene. Furthermore, a plausible reaction network was proposed.
研究领域:
催化化学
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可再生化学品
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产品关联
DOI
高影响因子
Sustainable Energy & Fuels
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2022
·Vol. 6
·期 10
·2449-2461
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IF 6.813
Hongxing Wang,Yueqing Wang,Long Huang,Anying Geng,Fengjiao Yi,Yulei Zhu,Yongwang Li
Highly efficient synthesis of 1,4-pentanediol (1,4-PDO) from industrialized biomass-based products is still a challenge due to the inherent chemical stability of intermediate product γ-valerolactone. The aim of the present research was to evaluate the influence of the synthetic conditions of CuMgAl layered double hydroxides on their physicochemical properties as well as catalytic performance in pure ethyl levulinate hydrogenation to produce 1,4-PDO in fixed-bed reactors. Systematic characterization results demonstrated that the CuMgAl catalyst prepared with mixed alkali as the precipitant has appropriate amounts of acid-base sites and a higher electron cloud density of Cu, which could well activate the carbonyl functional groups in the substrate molecule, and thus excellent reaction performance can be obtained. Ultimately, two-stage-packed dual solid catalysts in fixed-bed reactors were designed for one-step conversion of industrial furfuryl alcohol (FOL) to 1,4-PDO through an alcoholysis hydrogenation integrated continuous process. 94.3% yield of 1,4-PDO can be obtained from FOL in this effective tandem reaction.
研究领域:
生物化学
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催化化学
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产品关联
DOI
高影响因子
Green Energy & Environment
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2023
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IF 13.3
Lin Yuan,Yancheng Hu,Guangyi Li,Fengan Han,Aiqin Wang,Yu Cong,Tao Zhang,Feng Wang,Ning Li
The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society. Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene. To reduce the dependence on the limited oil source, we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol (MPD), acrylate and crotonaldehyde as starting materials. The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate, flow aromatization over Pd/C catalyst, hydrolysis and catalytic aerobic oxidation (60% overall yield). The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO 2 H. Crotonaldehyde can also participate in the reaction, followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54% overall yield. Life cycle assessment implies that compared to conventional fossil process, our biomass-based routes present a potential in reducing carbon emissions.
研究领域:
生物化学
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绿色化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Sustainable Energy & Fuels
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2022
·Vol. 6
·期 3
·834-840
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IF 6.813
Chunwei Liu,Yancheng Hu,Guangyi Li,Aiqin Wang,Yu Cong,Xiaodong Wang,Tao Zhang,Ning Li
Decalins are the main component of JP-900, a coal-based thermal stable advanced aviation fuel. Meanwhile, these compounds are also widely used as additives to improve the volumetric heat value and thermal stability of aviation fuels. Herein, a brand new three-step route was developed for the synthesis of renewable alkylated decalins from 2-methyl-2,4-pentanediol (MPD) and p-quinone, two platform compounds that can be derived from lignocellulose. First, a mixture of C6 dienes was obtained from the dehydration of 2-methyl-2,4-pentanediol under the catalysis of choline chloride (ChCl) based acidic deep eutectic solvents (DES). Among the investigated reaction media, the ChCl/MSA DES prepared with ChCl and methanesulfonic acid (MSA) demonstrated the highest activity and selectivity for the dehydration of MPD. This can be rationalized by the relatively higher acid strength of the MSA. By the Diels–Alder reaction of C6 dienes and p-quinone, C12 cycloadducts with double six-membered ring carbon chain structures were formed in the absence of any catalyst. Finally, the C12 cycloadducts were further hydrodeoxygenated to alkylated decalins with high-density (0.91 g mL−1) and low freezing point (225–236 K) over a physical mixture of Pd/C and H-Y zeolite.
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
DOI
高影响因子
Molecular Catalysis
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2023
·
IF 4.6
Bo Li,Haijun Guo,Zhen Xiong,Lian Xiong,Shimiao Yao,Mengkun Wang,Hairong Zhang,Xinde Chen
γ-valerolactone (GVL) is a sustainable chemical, which can be obtained by hydrogenation of levulinic acid (LA) and levulinate. Herein, we reported a solvent-free hydrogenation of butyl levulinate (BL) to GVL and 1,4-pentanediol (1,4-PDO) over a skeletal Cu-Al-Zn catalyst. The skeletal Cu-Al-Zn catalyst was prepared from Devarda's alloy by alkali leaching and the catalyst was characterized by different analysis methods. The aluminum in the Devarda's alloy was dissolved by sodium hydroxide in the leaching process and many active Cu atoms were generated on the catalyst surface and the skeletal Cu-Al-Zn exhibited many micrometer-scale irregular particles with rough surface. The skeletal Cu-Al-Zn catalyst showed the excellent performance in the solvent-free hydrogenation of BL to GVL under constant hydrogen pressure (5 wt% catalyst loading, 180°C, 6 MPa of H 2 , 6 h): the LA conversion was 100%, the GVL yield was 74.75% and the 1,4-PDO yield was 25.63%. Moreover, the catalyst showed stable performance and it was reusable up to 5 times without apparent loss of activity. A stable hydrogen pressure with Zn would suppressed the dehydration of 1,4-PDO.
研究领域:
催化
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绿色化学
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可持续化学
✓ 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）