JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2025
·
IF 6.2
Hengshuo Gu,Ting Zhao,Jian Li,Yufei Gu,Hucheng Ge,Yuke Liu,Fuwei Li,Zhixia Li,Hongfei Lin,Jiangfei Cao
Hierarchical ZSM-5 (Z-40) was synthesized via a simple two-step hydrothermal crystallization without using any organic template. Low-density polyethylene (LDPE) as hydrogen donor was added into the catalytic pyrolysis of cellulose to enhance deoxygenation and the formation of BTX (benzene, toluene, xylene). Cellulose and LDPE showed the strongest synergistic effect at a feed ratio of 1, and the obtained experimental BTX yield (22.9 %) was 52.7 % higher than the theoretical yield (15 %). Co-catalytic pyrolysis (CCP) of two polymers followed similar cracking behavior to CCP of their pyrolysis vapor model compounds (furfural and n -octane), mainly including pyrolysis, catalytic cracking of pyrolysis fragments in external surface and hydrocarbons pool reactions of small cracking fragments in the internal micropores of zeolite. Z-40 showed better catalytic performance than the commercial ZSM-5 (higher BTX yield and less coke deposition) due to the appropriate acidic properties and distinctive pore structure. The optimal condition for CCP of cellulose/LDPE was temperature at 550 °C, feed ratio at 1:1 and catalyst/feed ratio at 2:1, and the achieved BTX yield reached 24.5 % with high BTX selectivity of 86.7 %. This work provided a cost-effective method for synthesis of ZSM-5 and production of high value-added BTX via a green non-oil route.
研究领域:
化学工程
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能源科学
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2019
·
IF 3.375
Zhi-Cong Wang,Pei-Gao Duan,Xiao-Jie Liu,Feng Wang,Yu-Ping Xu
The low-boiling-point distillate (LBD) via vacuum distillation of biocrude produced from hydrothermal liquefaction of soybean straw was hydrotreated to produce trace-sulfur liquid fuel. The effects of five hydrogen donor solvents (HDSs), including cyclohexene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and Indane, on heteroatom removal efficiency were examined at 350 °C for 2 h with 6 MPa H2 added and 5 wt %(Pt/C)/feed. The LBD to HDS mass ratio was 1:1. HDSs not only could reduce the production of solid and gas and increase the yield of upgraded oil but also could favor denitrogenation, desulfurization, and deoxygenation of the upgraded oil. Among the HDSs examined, decahydronaphthalene showed the best performance for denitrogenation, and tetrahydronaphthalene was the most suitable HDS for deoxygenation and desulfurization. By employing a decahydronaphthalene and tetrahydronaphthalene mixture (w/w, 1:1) as the reaction medium, the effects of temperature (300–450 °C), time (1–6 h), H2 pressure (0.1–10 MPa), and Pt/C loading (0–20 wt %) on the product yields and quality of the upgraded oil produced from hydrotreating the LBD were examined. The upgraded oil was the dominant product fraction under all tested reaction conditions and varied between 76.7 and 87.3 wt %. The HDS mainly acted as a hydrogen transfer agent in the LBD hydrotreatment process, during which the HDS provided the hydrogen for the hydrogenation reaction, and this consumed hydrogen was resaturated by the external hydrogen source. A more positive synergistic effect was observed for the removal of N, O, and S when using the decahydronaphthalene and tetrahydronaphthalene mixture than when using decahydronaphthalene or tetrahydronaphthalene alone. N was the most difficult heteroatom to remove, followed by O and S. Catalyst loading was the most influential factor affecting the N, O, and S removal efficiencies. Under optimal reaction conditions, 93% of N, 95% of O, and 99% of S in the LBD and HDS blend were removed, which corresponded to contents of 0.05 wt %, 0.42 wt %, and 21 ppm in the upgraded oil, respectively. The equilibrium restrictions on denitrogenation, deoxygenation, and desulfurization were essential factors affecting the removal efficiencies of heteroatoms.
研究领域:
能源生物学
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化学工程
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Jian Wei,Yucui Hou,Tianqi Huang,Aohua Zheng,Shuhang Ren,Weize Wu
Identifying the source of products in lignin hydro-liquefaction oil is crucial for assessing the lignin conversion efficiency. The utilization of hydrogen donor solvents (HDSs) complicates the determination of whether polycyclic aromatic hydrocarbons (PAHs) derive from lignin or HDS. Thus, identifying the source of PAHs in the oil can improve our understanding of lignin structures and enhance its utilization. To address this challenge, 1,2,3,4-tetrahydroquinoline (THQ) was used as an HDS to trace products within the oil. The results showed that (1) lignin could be completely liquefied in THQ under optimal conditions: a THQ/lignin mass ratio of 0.5, a reaction temperature of 450 °C, an initial H2 pressure of 8 MPa, a reaction time of 4 h, and a molybdenum sulfide/lignin mass ratio of 1; (2) PAHs with 2–6 rings were identified in the oil and confirmed to derive solely from lignin through qualitative and quantitative analyses via GC–MS rather than THQ.
研究领域:
能源化学
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环境科学
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生物质转化
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2022
·
IF 8.943
Jiaman Sun,Juan Luo,Rui Ma,Junhao Lin,Lin Fang
In order to reduce the risks of sulfur-containing contaminants present in biofuels, the effects of microwave and content of hydrogen donor on the cracking of C–S bonds and the migration of sulfur were studied by co–pyrolysis of biomass and plastic. The synergistic mechanism of microwave and hydrogen donor was explored from the perspective of deducing the evolution of sulfur–containing compounds based on microwave thermogravimetric analysis . By combining temperature–weight curves, it was found that microwaves and hydrogen radicals promoted the cracking of sulfur–containing compounds and increased the mass loss of biomass during pyrolysis . The mixing ratio of hydrogen donor (plastic) was the key parameter resulting in the removal of sulfur from oil. By adjusting the mixing ratio, the yield of co–pyrolyzed oil was three times higher than that of cow dung pyrolysis alone and the relative removal rate of sulfur reached 73.67%. The relative content of sulfur in the oil was reduced by 73.77% due to the escape of sulfur–containing gases (H 2 S, COS and C 2 H 5 SH) and the formation of sulfate crystals in the char. Microwave selectively heated sulfur–containing organics and hydrogen radicals stimulated the breaking of C–S bonds, which improved the cracking efficiency of the oil. This breaking will provide a theoretical and technological reference for the environmentally friendly treatment of biomass and biofuels.
研究领域:
能源与环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2023
·
IF 6
Hong-Jun Lu,Dong-Hao Yuan,Chang Gao,Bi-Cheng Li,Zi-Bin Huang,Jing-Yi Yang,Pei-Qing Yuan
The effect of the timing of adding 1 wt% decalin as a hydrogen donor on heavy oil visbreaking was studied. Experiments show that either premixing decalin with heavy oil or adding decalin during the reaction accelerates the formation of light distillates and improves the efficiency of viscosity reduction. Premixing with heavy oil is an appropriate way to add decalin. After 10 min of reaction at 400 ℃, the viscosity reduction rate of the product reaches 90% and the asphaltene content of the product is 1.8 wt% lower than that of the raw heavy oil. According to theoretical calculations, the active hydrogens of decalin preferentially saturate the aromatic C radicals that are critical for condensation . The equilibrium constant of the H-donation reaches the order of 10 5 , while the activation energy of the reaction is only about 26 kJ/mol. The thermal cracking of decalin itself releases active and small-sized radicals, which accelerate visbreaking by participating in the dealkylation network of heavy oil molecules.
研究领域:
石油工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED ENERGY
·
2024
·
IF 10.1
Fawei Lin,Chujun Luan,Huiyi Mao,Chenxu Zhong,Xinlu Han,Guanyi Chen,Lei Che
The petroleum industry and pyrolysis of organic solid waste produce a large amount of low-grade fuel oil characterized by high proportions of heavy fractions, unsaturated compounds, and oxygen content. Catalytic hydro-pyrolysis is an effective approach to improve the quality with co-production of valuable pyrolysis gases and high-grade pyrolysis oils. However, exploration of available and low-cost hydrogen donors is the determining factor for the feasibility of this technique. Given that NH 3 is the excellent hydrogen carrier and with an active molecular structure, this work innovatively proposed NH 3 assisted catalytic pyrolysis that could significantly promote hydrogenation and cleavage reactions to acquire high-quality products and efficient utilization of NH 3 energy. HZSM-5 with specific modification by desilicication and phosphorus loading was selected as the optimal catalyst. The abundant hierarchical pore structure and weak acidity mainly contributed to the excellent catalytic performance. Specifically, 3 + rings aromatics (≥3 rings) disappeared, long-chain alkanes decreased by 10.45 %, while short-chain alkanes increased from 0 to 42.05 % for HO pyrolysis at 550 °C. The stability and universality of this approach were respectively investigated. Meanwhile, the heat value of pyrolysis gas increased by 3766 times under the optimal condition mainly due to the distinctly high yield of C 2 -C 4 combustible hydrocarbons, ca. 429.22 mL/g-oil. Accordingly, the pyrolysis gas could reach the target of energy self-supply for pyrolysis process by in-situ combustion with the residual NH 3 . Additionally, simulation calculations demonstrated that co-combustion of NH 3 and pyrolysis gases increased the laminar burning velocity and enhanced the combustion efficiency of NH 3 . Approximately 37,675 kJ/kg-oil energy could be produced in gas during NH 3 assisted catalytic pyrolysis to provide sufficient heat in pyrolysis with zero natural gas input. Extremely low production of CO 2 , zero natural gas input, and abundant C 2 -C 4 hydrocarbons jointly promoted the negative carbon effect, ca. 948.65 L CO 2 -eq./kg-oil. This study aims to propose NH 3 as a hydrogen donor so that low-grade fuel oil can be upgraded with energy self-supply.
研究领域:
化学工程
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能源科学
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产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2019
·Vol. 26
·期 10
·9480-9489
·
IF 2.914
Dai Shijin,Zheng Yilin,Zhao Youcai,Li Qiang,Niu Dongjie
Chlorine-containing organic waste (COWs) is a big threat for the waste incineration because of the dioxin generation and equipment corrosion. Recently, dechlorination and detoxification of COWs is emergent in order to lower the environmental risk and treatment costs. In this study, base-catalyzed decomposition processes with different hydroxides, hydrogen donors, and catalysts were conducted for pre-treatment of COWs to reduce organic chlorine content, with the TCB as a model compound and industrial rectification residues for verification. Results showed that maximum chlorine retention efficiency (CRE) of four alkalis followed the order of KOH > NaOH–KOH > NaOH > Mg(OH) 2 , which were 98.3%, 93.4%, 97.2%, and 1.5%, respectively, and could be expressed as an apparent first-order reaction. The differences were resulted from the varying ionic potentials of the metal cations. Hydrogen donors (glycol, glycerol, paraffin oil, and PEG 200) acted as effective dechlorination regents follow the order of PEG > glycol > paraffin oil > glycerol. In addition, Fe, Ni, Cu, and activated carbon catalysts increased the CRE by 68.9% to 92.4%, 91.9%, 89.2%, and 73.3%, respectively. Residue analysis through X-ray diffraction and Fourier transform infrared spectroscopy revealed that KCl, sodium oxalate, and phenol were the main products and a plausible stepwise dechlorination pathway was proposed. The effectiveness of three optimized combinations including NaOH/PEG, KOH/PEG, and NaOH–KOH/PEG (with the Fe catalyst) was confirmed by using them for dechlorinating rectification residues, and they restrained 98.2%, 91.2%, and 94.6% of the chlorine, respectively. The organochlorine content decreased from 19.2 to 1.8% within 180 min, while inorganic chorine content increased from 1.5 to 18.9%, indicating the potential for COWs dechlorination.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Processes
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2025
·Vol. 13
·期 4
·1110
·
IF 2.8
Shikang Zhao,Guohong Chen,Kaiqi Zheng,Shaojie Li,Jiaqi Xu,Fanan Wang,Xueping Liu,Rengui Weng
γ-Valerolactone (GVL) is a promising bio-based platform molecule with significant potential for energy applications. The production of GVL via biomass-based levulinic acid (LA) is an important reaction. To enhance the conversion and selectivity of non-precious-metal catalysts in the LA-to-GVL process and to better understand the key factors influencing this conversion, we conducted a series of experiments. In this study, supported Cu-Ni bimetallic catalysts (Cu-Ni2/Al2O3) were prepared using layered double hydroxides (LDHs) as a precursor. Compared with Cu-Ni catalysts synthesized via the conventional impregnation method, the Cu-Ni2/Al2O3catalysts exhibit higher catalytic activity and stability. The results demonstrated that efficient conversion was achieved with isopropanol as the hydrogen donor solvent, a reaction temperature of 180 °C, and a reaction time of 1 h. The yield of GVL reached nearly 90%, with a decrease of approximately only 6% after six consecutive cycles. The Cu-Ni2/Al2O3catalyst proved to be effective for converting biomass-derived LA to GVL, offering a route that not only reduces production costs and environmental impact but also enables efficient biomass-to-energy conversion.
研究领域:
催化化学
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能源科学
·
生物质利用
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Bingyue Tang,Wenzhi Li,Xia Zhang,Baikai Zhang,Hao Zhang,Cunshuo Li
Depolymerization of Kraft lignin represents an attractive strategy to obtain alternatives to fossil fuels. In this work, via the controlled oxidation of MoS 2 precursor, an oxygen-vacancy-enriched MoO 3 was synthesized and employed to catalyze the depolymerization of Kraft lignin in a new solvent system without external H 2 gas. Systematic characterizations exemplified that the calcination temperature significantly affected the morphology and concentration of oxygen vacancy of prepared MoO 3 , and the appropriate temperature in this work was proved to be 350 °C. In the optimized hydrogen-donor solvent system that contained 20 mL 1, 4-dioxane, 20 mL isopropanol and 5 mL methanol, MoO 3 -350 catalyst gave a 87 wt% yield of petroleum ether soluble products, and the higher heating value (HHV) of liquid fuels (33.4 MJ/kg) was dramatically increased compared with the original Kraft lignin (25.23 MJ/kg). Methanol and isopropanol were analyzed to be capable of promoting the solubility of Kraft lignin and supplying hydrogen in the reaction system, respectively. Underpinned by characterizations and products analysis, the schematic representation of possible reaction pathway was given.
研究领域:
能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2021
·
IF 6.609
Zhi-Cong Wang,Dabo Chen,Ya-Qi Shan,Lin-Xin Lin,Pei-Gao Duan
In this study, a high-boiling point fraction (HBF, 141-220 °C) from vacuum distillation of a biocrude produced from hydrothermal liquefaction of soybean straw was hydrotreated in a hydrogen donor solvent (HDS) mixture consisting of tetralin and decalin at a mass ratio of 1:1. Effects of temperature (300–450 °C), time (1–6 h), H 2 pressure (0.01–10 MPa), and Pt/C loading (0–40 wt%) on the products distribution and properties of the treated oil were examined. Increasing the temperature, time, and catalyst loading or decreasing the H 2 pressure would reduce the treated oil yield and increase the gas and solid product yields. The presence of HDS mixture played a critical role in favoring the production of treated oil, reducing the formation of gas and solid products, and the removal of N, O, and S from the HBF. Under optimal reaction conditions, 96.3% of N, 87.1% of O, and 98.5% of S were removed from the initial feedstock. The treated oil mainly consisted of saturated hydrocarbon(∼40%, C8-C20) and aromatics(∼41%, naphthalene and benzene derivatives), which was had a comparable cetane number and better combustion characteristics relative to the market 0# diesel.
研究领域:
能源生物学
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化学工程
✓ 已验证
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
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
BIOMASS & BIOENERGY
·
2024
·
IF 5.8
Linhua Song,Yushan Jiang,Zhengzheng Zhang,Yuqing Ouyang
Hydrogen-supplied liquefaction technology is considered to be one of the most essential thermal treatment strategies for improving the quality of bio-oil. This study employed wood chips as feedstock, inert alkanes as dispersing solvent, and tetraline as hydrogen donor. The yields of bio-oil rose substantially from 45.2% to 69.2% and 68.3% with CaO and 8% NiO/γ-Al 2 O 3 catalysts, respectively, at 310 °C for 30 min with a ratio of wood chips to n -heptane of 1:8 g ml −1 . The reaction mechanism was examined using microcrystalline cellulose and lignin as model compounds. Tetralin offered the active hydrogen, while the strong alkalinity of CaO brought about high-temperature fragmentation of cellulose to produce small-molecule ethers, aldehydes, and ketones. These species would eventually transform into alcohols through engaging with the active hydrogen. The introduction of NiO/γ-Al 2 O 3 promoted the ring-forming reaction of cellulose-derived fragments, resulting in an increase of furan content (up to 29.97%). This phenomenon suggested that the varied catalysts exerted a remarkable impact on the hydrogen-supplied liquefaction of cellulose. The catalytic effect on lignin was evident in the breakage of the C–O bond in the side chain of phenol, leading to the generation of an impressive amount of phenolics. In light of changes in the generated products and calculation of the theoretical bond energies, the bond-breaking approaches and potential reaction pathways of biomass impacted by different catalysts were proposed, providing a theoretical foundation for the development and application of biomass energy.
研究领域:
能源植物学
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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）