FUEL PROCESSING TECHNOLOGY
·
2014
·
IF 3.019
Wen Chen,Zhongyang Luo,Chunjiang Yu,Yi Yang,Guoxiang Li,Jixiang Zhang
In this paper, guaiacol was used as a model compound of bio-oil and its catalytic conversion was carried out in ethanol. The effect of supports (SBA-15, ZrO 2 /SBA-15 and SO 4 2 − /ZrO 2 /SBA-15) was studied on Pt–Ni based catalysts whereas the effect of active metals was investigated over C-supported Ru, Pt and Pd catalysts. Among the tested catalysts, Ru/C showed the best performance of total guaiacol conversion with high selectivity towards the desired products, cyclohexanol and 2-methoxycyclohexanol (MCH). The reaction pathways of guaiacol in ethanol were clarified based on the product analysis. With the catalysis of Ru/C, the effects of reaction temperature, initial hydrogen pressure, and other typical compounds from bio-oil were investigated. Temperatures had negligible effect on both the conversion of guaiacol and the yields of desired products in the range of 140–260 °C. Guaiacol conversion decreased significantly at initial hydrogen pressures lower than 4.0 MPa. The presence of furfural , acetone , and acetic acid decreased the conversion of guaiacol dramatically while the addition of water had a smaller impact. Further work revealed that the mass and energy efficiency of converting guaiacol into MCH are 100% and 97%, respectively.
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
FLUID PHASE EQUILIBRIA
·
2016
·
IF 1.846
Xiaoxiao Sheng,Qinbo Wang,Zhenhua Xiong,Chuxiong Chen
The solubilities of adipic acid in cyclohexanone + cyclohexanol mixtures at (303.15–349.45) K, in cyclohexane + cyclohexanol mixtures at (304.15–339.45) K, and in cyclohexane + cyclohexanone mixtures at (304.85–342.45) K were determined at atmospheric pressure by the dynamic method. Experimental results show that when solvent composition remains constant, solubilities of adipic acid in the studied binary mixed solvents increase monotonically with temperature increasing, and when temperature remains constant, solubilities of adipic acid decrease monotonically with the increasing mass fraction of cyclohexane in cyclohexane + cyclohexanol and cyclohexane + cyclohexanone mixture. However, the measured solubility firstly increases monotonically with the increasing mass fraction of cyclohexanone in cyclohexanone + cyclohexanol mixtures and then reaches the maximum solubility at the mass fraction of cyclohexanone at 0.4. When the mass fraction of cyclohexanone was bigger than 0.40, the solubility of adipic acid decreased with the increasing mass fraction of cyclohexanone. There exists a maximum-solubility effect. Further, both the NRTL equation and the Apelblat equation were used to correlate the experimentally determined solubilities. A fairly good agreement was obtained between the correlated solubilities with the experimental observations. Thermodynamic quantities of dissolution were calculated by the Clark and Glew equation, including dissolution enthalpy, entropy, Gibbs energy and isobaric heat capacity for adicip acid in cyclohexane + cyclohexanol, cyclohexane + cyclohexanone, and cyclohexanone + cyclohexanol solvent mixtures .
研究领域:
化学工程
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热力学
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DOI
高影响因子
FLUID PHASE EQUILIBRIA
·
2015
·
IF 2.2
Yinchuan Pei,Qinbo Wang,Xing Gong,Fuqiong Lei,Binwei Shen
Liquid–liquid equilibrium (LLE) data for ternary systems water + cyclohexane + cyclohexanol and water + cyclohexane + cyclohexanone were measured at (303.2–333.2) K and under atmospheric pressure. The reliability of the experimental tie-line data was checked by the empirical Othmer–Tobias correlation. The distribution coefficient and separation factor were used to investigate the distribution of cyclohexanol and cyclohexanone between water and cyclohexane. The results show that the distribution coefficient of cyclohexanol or cyclohexanone between organic and aqueous phases increases with the increasing content of cyclohexanol or cyclohexanone in water, and so does it with the increasing of temperature. By using the NRTL and UNIQUAC activity coefficient models, the experimentally determined LLE data, along with the LLE data for another ternary system water + cyclohexanol + cyclohexanone [G. Xing, W. Qinbo, L. Fuqiong, S. Binwei, J. Chem. Eng. Data 59 (2013) 1651–1655], were correlated simultaneously. Good agreements were obtained between the correlated and experimentally determined tie-line data. The binary NRTL and UNIQUAC interaction parameters were obtained. Furthermore, four sets of quaternary LLE data for water + cyclohexane + cyclohexanol + cyclohexanone were experimentally determined at 318.2 K. The experimentally determined quaternary LLE data were compared with the NRTL model predicted LLE data, and generally agreements were obtained. It further verifies the reliability of the obtained binary model parameters, and indicates the obtained parameters could be used for prediction, as well as design and optimization of the related separation process.
研究领域:
化学工程
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物理化学
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2016
·
IF 1.835
Xiaoxiao Sheng,Qinbo Wang,Linhui Chen,Zhipeng Shen,Yinchuan Pei
The solubilities of glutaric acid in binary cyclohexane + cyclohexanol solvent mixtures at 298.05–343.65 K, in binary cyclohexane + cyclohexanone solvent mixtures at 299.10–340.65 K, in binary cyclohexanone + cyclohexanol solvent mixtures at 299.75–343.65 K, and in ternary cyclohexanol + cyclohexanone + cyclohexane solvent mixtures at 298.15–330.95 K were studied by the dynamic method. The results show that the solubility of glutaric acid increases as temperature increases at constant solvent composition in three determined binary solvent systems. For binary cyclohexane + cyclohexanol and cyclohexane + cyclohexanone solvent mixtures, solubilities of glutaric acid decrease monotonically with the increasing mass fraction of cyclohexane in solvent mixtures at constant temperature. However, for binary cyclohexanone + cyclohexanol solvent mixtures, cyclohexanone with a mass fraction at 0.6 in solvent mixtures has the best dissolving capacity for glutaric acid at constant temperature. The experimental solubility data of three determined binary solvent systems were correlated by the Apelblat equation and nonrandom two-liquid (NRTL) activity coefficient model, and the correlated solubilities data were in good accord with the experimental data. The obtained binary interaction parameters for the NRTL model were used to calculate the solubilities of glutaric acid in the ternary cyclohexanol + cyclohexanone + cyclohexane solvent mixtures, which were compared with the experimental solubilities data.
研究领域:
化学工程
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物理化学
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Xiaoting Xing,Wenlong Cao,Jinliang Yan,Yuchun Zhang,Payam Ghorbannezhad,Zhiyu Li,Peng Fu
Cyclohexanol is a crucial intermediate in the synthesis of nylon and other chemical industry materials. However, directly hydrogenating phenol to cyclohexanol presents challenges, including harsh reaction conditions and low selectivity for the desired product. To address these issues, a two-step method was proposed, involving the mild catalytic decoupling and hydrogenation of lignin, which enables the efficient production of cyclohexanol. Lignin was initially depolymerized into 18.08 % phenol and 60.63 % guaiacol in a dilute alkaline aqueous solution at 200°C under atmospheric nitrogen. Subsequently, the effects of catalytic hydrogenation of phenol in different solvents were examined. When water was used as the solvent, phenol conversion reached 100 % within 2 hours at 30°C, with a selectivity of 94.69 % to cyclohexanol. The hydrogenation process, catalyzed by 5 wt% Pd/AC, was studied under these conditions. It was found that phenol was first partially hydrogenated to cyclohexenol, which quickly isomerized to cyclohexanone and was further hydrogenated to cyclohexanol. The two steps create a low-temperature and low-pressure pathway for efficiently converting lignin to cyclohexanol, thereby enhancing lignin's potential value.
研究领域:
化学工程
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生物质转化
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催化科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2021
·
IF 4.311
Yong Suo,Yongsheng Ren
The influence of representative typical pollutants in the zero-discharge process of coal chemical high-salty wastewater on the fouling behavior of nanofiltration membranes was studied. In this study, a commercially available NF90 nanofiltration membrane was selected, with three inorganic salts, cyclohexanol (C 6 H 12 O) and APAM as the main target foulants. Various membrane samples were characterized by Contact angle, AFM and SEM-EDS, and the membrane fouling behavior was quantitatively evaluated by analyzing the influence of the interaction between different components in the feed solution on the membrane flux and interface thermodynamics. The results show that the deposition of fouling is closely related to the interface free energy (ΔG). The AB interfacial energy significantly affects membrane fouling. Membrane fouling is mainly dominated by residual APAM, followed by inorganic salts and cyclohexanol. The interaction between organic and inorganic fouling is the core factor that exacerbates membrane fouling. The interaction between APAM and inorganic salt ions mainly accelerates membrane fouling through charge shielding and complexation. Cyclohexanol accelerates membrane fouling mainly by reducing the solubility of inorganic salts and absorbing on the surface of the fouling layer. The competition and synergy between hydrophilic APAM and hydrophobic cyclohexanol are also the factors that aggravate membrane fouling.
研究领域:
环境科学
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化学工程
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DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 3
·1152-1164
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IF 10.182
Jiahui Zhan,Rui Hu,Xi Luo,Cheng Zhang,Gang Luo,Jiajun Fan,James H. Clark,Shicheng Zhang
Cyclohexanol is an essential intermediate in the chemical industry for the synthesis of nylon and other materials, but the direct hydrogenation of phenol to produce cyclohexanol is problematic owing to excessive energy consumption associated with the harsh reaction conditions. In this regard, novel composite catalysts (Ru/Nb2O5-nC18PA) coated with octadecylphosphonic acid (C18PA) were prepared via an impregnation method to be applied for the efficient hydrogenation of phenol to produce cyclohexanol in a biphasic system consisting of water and decalin solvent. Under a hydrogen pressure of 12 bar and 80 °C, nearly 100% conversion of phenol and 93% yield of cyclohexanol were achieved within 4 hours. With the introduction of more Lewis acid sites the aromatic ring is activated, which promotes the HYD (hydrogenation) path of phenol, thereby giving improved selectivity to cyclohexanol. A mechanism-exploration experiment was carried out and showed that the strong binding effect between the surface of the Ru/Nb2O5-nC18PA catalysts and the benzene ring allows the aromatic ring in phenol to be hydrogenated, increasing the selectivity to cyclohexanol. This biphasic catalytic system enhances the potential value of lignin via the catalytic hydrogenation of lignin-derived phenols.
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 CHEMICAL AND ENGINEERING DATA
·
2018
·
IF 2.196
Xiaoxiao Sheng,Weiping Luo,Qinbo Wang
The solubilities of succinic acid in binary cyclohexanone + cyclohexanol solvent mixtures at 304.25–354.65 K, in binary cyclohexane + cyclohexanol solvent mixtures at 300.15–346.15 K, in binary cyclohexane + cyclohexanone solvent mixtures at 297.65–351.25 K, and in ternary cyclohexanol + cyclohexanone + cyclohexane solvent mixtures at 306.95–343.15 K were determined by the synthetic method at atmospheric pressure. The experimental solubility data in binary solvent mixtures were correlated by the Apelblat equation and nonrandom two-liquid (NRTL) activity coefficient model, and the calculated solubility data by the models have a good agreement with the experimental data. Then, the solubilities of succinic acid in ternary cyclohexanol + cyclohexanone + cyclohexane solvent mixtures were predicted by the NRTL model and compared with the experimental solubility data. Finally, the solubilities of succinic acid in the three studied binary solvent mixtures were compared with the solubilities of glutaric acid and adipic acid in the same solvent systems at 303.15–343.15 K. The result shows that in the three studied solvent mixtures, glutaric acid with an odd number of carbon atoms is much more soluble than succinic acid and adipic acid with an even number of carbon atoms. The reasons for this “odd–even effect” phenomenon are the interlayer packing of molecule chains and the twist of the carbon chains.
研究领域:
化学工程
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物理化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yuying Zhao,Jiahui Zhan,Rui Hu,Gang Luo,Jiajun Fan,James H. Clark,Shicheng Zhang
Extensive use of grey hydrogen in traditional hydrodeoxygenation (HDO) severely reduces the sustainable development of lignin valorization processes. Conversely, the catalytic transfer hydrogenation (CTH) mediated by green hydrogen is an alternative strategy that promotes the sustainability of in-situ hydrogenation of lignin. In this work, a bifunctional catalyst (Ru/NiAl 2 O 4 ) was developed to assist the proposed green hydrogen-driven cosolvent system composed of isopropanol and water for the CTH of guaiacol. Results indicate that 95% conversion of guaiacol and 80% cyclohexanol selectivity can be achieved at 200 ℃ within 3 h with a high water/isopropanol ratio (6/4), significantly increasing the greenness and sustainability. Furthermore, the recycling experiments verify the stability of the catalyst’s active sites. Analysis of the mechanism suggests that the high efficiency of such system can be attributed to the activation of metal and acid dual functional sites of Ru/NiAl 2 O 4 catalyst on aromatic rings and C-O bonds. The acceleration of the in-situ hydrogen supply is due to hydrogen exchange between water and isopropanol. The participation of water in the reaction is also demonstrated by the presence of deuterium in the product after the reaction in D 2 O. This work provided the insights into the development of a strategy for the production of cyclohexanol from lignin derivatives by an in-situ CTH system.
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
FUEL
·
2022
·
IF 8.035
Tao Liu,Zhipeng Tian,Weijie Zhang,Bowen Luo,Libin Lei,Chao Wang,Jianping Liu,Riyang Shu,Ying Chen
Selective hydrodeoxygenation (HDO) of phenolic compounds derived from the pyrolysis lignin-oil to desired products is a promising route in the high-value utilization of biomass-derived products. Cyclohexanol, as one of the important chemical materials, is an intermediate of catalytic HDO of guaiacol. Controllable selective HDO is conducted to improve the cyclohexanol selectivity over RuFe bimetallic catalyst prepared by ethylene glycol reduction method in this work. 99.99% guaiacol conversion and 81.35% cyclohexanol selectivity are obtained over optimized 2Ru2.5Fe/Al 2 O 3 -EG catalyst, which is better than those over 2Ru/Al 2 O 3 -EG catalyst. The mild catalyst preparation method gives it a high dispersion and uniform distribution of Ru and Fe species on the support. Various characterizations have proved that the intimate contact between Ru and Fe 2 O 3 species contributes to the improvement of cyclohexanol selectivity. Partial blockage of Ru sites by Fe 2 O 3 species slightly reduces the hydrogen adsorption capacity while the addition of Fe helps enhancing the hydrogenolysis of C-OMe bond. The reciprocal effect facilitates the removal of methoxyl groups and hinders the dehydroxylation of cyclohexanol to cyclohexane. Besides, other phenolic compounds and pyrolysis lignin-oil as substrates also show good selective HDO reactivity to corresponding alkyl cyclohexanols, implying potential application in the transformation from lignin-oil to high-value products.
研究领域:
催化
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化学工程
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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
Journal of Energy Chemistry
·
2023
·
IF 13.1
Baoyu Wang,Peng Zhou,Ximing Yan,Hu Li,Hongguo Wu,Zehui Zhang
In this work, a dual-size MOF-derived Co catalyst (0.2Co 1-NPs @NC) composed of single atoms (Co 1 ) and highly dispersed nanoparticles (Co NPs) was prepared by in-situ Zn evaporation for the high-performance conversion of lignin-derived o- methoxyphenols (lignin oil) to cyclohexanols (up to 97% yield) via cascade demethoxylation and dearomatization. Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process, in which the Co NPs could initially dissociate hydrogen at lower energies while Co 1 remarkably facilitated the cleavage of the C Ar − OCH 3 bond. Moreover, the intramolecular hydrogen bonds formed in the o -methoxy-containing phenols were found to result in a decrease in the bond energy of the C Ar − OCH 3 bond, which was more prone to be activated by the dual-size Co sites. Notably, the pre-hydrogenated intermediate (e.g., 2-methoxycyclohexanol from guaiacol) is difficult to undergo demethoxylation, indicating that the selective C Ar − OCH 3 bond cleavage is a prerequisite for the synthesis of cyclohexanols. The 0.2Co 1-NPs @NC catalyst was highly recyclable with a neglect decline in activity during five consecutive cycles. This cooperative catalytic strategy based on the metal size effect opens new avenues for biomass upgrading via enhanced C O bond cleavage of high selectivity.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 5
·1-10
·
IF 4.3
Li Kaile,Yu Shijie,Li Qinghai,Zhang Yanguo,Zhou Hui
Lignin, an abundant aromatic polymer in nature, has received significant attention for its potential in the production of bio-oils and chemicals owing to increased resource availability and environmental issues. The hydrodeoxygenation of guaiacol, a lignin-derived monomer, can produce cyclohexanol, a nylon precursor, in a carbon-negative and environmentally friendly manner. This study explored the porous properties and the effects of activation methods on the Ru-based catalyst supported by environmentally friendly and cost-effective hydrochar. Highly selective cleavage of C aryl -O bonds was achieved under mild conditions (160 °C, 0.2 MPa H 2 , and 4 h), and alkali activation further improved the catalytic activity. Various characterization methods revealed that hydrothermal treatment and alkali activation relatively contributed to the excellent performance of the catalysts and influenced their porous structure and Ru dispersion. X-ray photoelectron spectroscopy results revealed an increased formation of metallic ruthenium, indicating the effective regulation of interaction between active sites and supports. This synergistic approach used in this study, involving the valorization of cellulose-derived hydrochar and the selective production of nylon precursors from lignin-derived guaiacol, indicated the comprehensive and sustainable utilization of biomass resources.
研究领域:
化学工程
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环境科学
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DOI
高影响因子
危险品化学品经营许可证（带存储）