Biomass Conversion and Biorefinery
·
2021
·Vol. 12
·期 8
·3503-3511
·
IF 4.987
Huang Xin,Xu Anbang,Bu Xinyuan,Huang Yong,Ran Jingyu
Levoglucosenone (LGO), derived from catalytic pyrolysis of cellulose, has shown its potential as a bio-renewable platform for the production of fine and commodity chemical. In this study, we report a biphasic system for conversion of LGO to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) with a substantial yield. The hydrolysis parameters, including single-biphasic phase, catalyst, temperature, and reaction time, were investigated on LGO conversion, respectively. The results showed that NaCl/H 2 O-MIBK biphasic system led to a profoundly increase of HMF selectivity by 37% compared to aqueous phase. An increase of acid site significantly enhanced LGO conversion and meanwhile promoted overreaction of HMF to LA and humins. Thus, HMF yield was observed firstly increased and then decreased with a maximum yield of 53.6% by using oxalic acid as a catalyst. The biphasic system effectively suppressed the humins formation and resulted in a maximum total HMF and LA yield of 86.7%.
研究领域:
化学工程
·
可再生资源利用
✓ 已验证
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Haiping Yang,Shuaishuai Lei,Kun Xu,Yang Fang,Xu Chen,Yingquan Chen,Xianhua Wang,Hanping Chen
In this study, a new method for the efficient preparation of levoglucosenone (LGO) by biomass catalytic pyrolysis with sulfonated carbon catalyst was proposed. The influence of pyrolysis temperature and the mass ratio of catalyst to glucose or cellulose on the formation of LGO was systematically studied. The results show that when the mass ratio of glucose to sulfonated carbon is 1:1 and the pyrolysis temperature increases from 300 °C to 500 °C, the LGO selectivity first increased and then decreased, reaching a maximum value of 46.4% at 400 °C. Meanwhile, the yield of LGO increased steadily with the increase in pyrolysis temperature, and the yield of LGO was reached a maximum value of 2.48 wt% at 500 °C. However, with the increasing amount of catalyst, the selectivity of LGO increased steadily, while the yield of LGO increased at first and then decreased. Overall, the optimum pyrolysis temperature and mass ratio of the glucose/sulfonated carbon catalyst for LGO production were 400 °C and 1:1, respectively. Density functional theory calculations showed that the catalytic action of sulfonated carbon changed the reaction pathway of glucose pyrolysis, making glucose more inclined to form LGO through a 1,2 dehydration mechanism.
研究领域:
生物质能
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2022
·
IF 6.449
Guangchuan Tang,Xin Huang,Anbang Xu,Zhongqing Yang,Changlei Qin,Jingyu Ran
Pyrolysis of cellulose produces substantial anhydrosugars, particularly levoglucosan (LGA), as the main product. In this study, liquid-phase continuous conversion of LGA was carried out over SO 3 H functionalized resin for the production of levogluosenone (LGO), which is a bio-renewable platform for fine and commodity chemicals. Factors including solvent, reaction temperature, catalyst dosage, initial LGA concentration and total flow rate were investigated on the influence of LGO yield, which was obtained with the highest yield of 38.4 % at 94.8 % LGA conversion at the optimized conditions. In addition, a stable catalytic performance without losing LGO yield was observed for 10 h long test. The use of glucose as substrate led to a decrease of LGO yield to 33.5 %, nevertheless, the use of bio-oil, derived from cellulose pyrolysis, as the substrate promoted LGO yield to 55.4 % due to the presence of other anhydrosugars. Density functional density calculations revealed that the free energy barrier was significantly decreased to 168 kJ/mol with the SO 3 H functionalized resin compared to that of 258 kJ/mol without catalyst.
研究领域:
生物化学
·
可再生资源与环境工程
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2024
·
IF 5.2
Xin Huang,Guangchuan Tang,Lei Tang,Chuan Ma,Yunlin Shao,Jingyu Ran
Bio-based platform chemicals are of great significance to future green fine and commodity chemicals. This study reports the performances and mechanisms of solvothermal dehydration of levoglucosan (LGA), the main precursor from noncatalytic pyrolysis of cellulose with a yield up to 80 wt %, to levoglucosenone (LGO) using cesium heteropolyacid salts at the catalyst in DMSO solvent. Catalyst characterizations revealed that cesium was well doped in the cubic of heteropolyacids, and the cesium doping ratio substantially influenced the catalytic performances toward LGO. LGO yield first increased and then decreased with the increase of cesium doping ratios, which is consistent with the change trends of pore structures and Brønsted/Lewis acid site ratios of the cesium heteropolyacid salts. LGO was obtained with the maximum yield at 41.2% over Cs2H2SiW12O40 compared to 39.2% over Cs2.5H0.5PW12O40. The catalyst can be regenerated by calcination without losing its catalytic performances. In addition, density functional theory calculation was used to reveal the mechanism for LGO formation, and the rate-determining step was the first step of the dehydration reaction with the energy barrier of 166 kJ/mol.
研究领域:
化学工程
·
可再生资源与环境科学
✓ 已验证
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2011
·
IF 4.365
Xian-wei Sui,Zhi Wang,Bing Liao,Ying Zhang,Qing-xiang Guo
Fast pyrolysis of bagasse pretreated by sulfuric acid was conducted in a fixed bed reactor to prepare levoglucosenone (LGO), a very important anhydrosugar for organic synthesis. The liquid yield and LGO yield were studied at temperatures from 240 to 350 °C and sulfuric acid loadings from 0.92 to 7.10 wt.%. An optimal LGO yield of 7.58 wt.% was obtained at 270 °C with a sulfuric acid pretreatment concentration of 0.05 M (corresponding to 4.28 wt.% sulfuric acid loading). For comparison, microcrystalline cellulose pretreated by 0.05 M sulfuric acid solution was pyrolyzed at temperature from 270 °C to 320 °C, and bagasse loaded with 3–5 wt.% phosphoric acid was pyrolyzed at temperature from 270 °C to 350 °C. The highest yield of LGO from bagasse was 30% higher than that from microcrystalline cellulose, and treatment with sulfuric acid allowed a 21% higher yield than treatment with phosphoric acid.
研究领域:
生物化学工程
·
可再生资源利用
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemSusChem
·
2010
·Vol. 4
·期 1
·79-84
·
IF 4.767
Zhi Wang,Qiang Lu,Xi-Feng Zhu,Ying Zhang
Graphical It′s not diamond, it′s zirconia: SO 4 2− /ZrO 2 is an efficient catalyst for the production of levoglucosenone by fast pyrolysis of cellulose admixing catalysts. The optimal temperature for preparation of levoglucosenone is in the range of 320–350 °C. In the presence of the SO 4 2− /ZrO 2 , the levoglucosenone content of pyrolysis liquid is greatly increased at 335 °C compared to pure cellulose. Sulfated zirconia was employed as catalyst for fast pyrolysis of cellulose to prepare levoglucosenone (LGO), a very important anhydrosugar for organic synthesis. The yield and the selectivity of LGO were studied in a fixed-bed reactor at different temperatures and cellulose/catalyst mass ratios. The experiments of catalyst recycling were also carried out. The results displayed that from 290 to 400 °C, the liquid and solid accounted for more than 95 wt % of products, and the higher temperature led to more liquid and less solid products. The introduction of SO 4 2− /ZrO 2 could promote cellulose conversion and LGO production. The temperature had a similar effect on the yield and selectivity of LGO at different cellulose/catalyst mass ratios. The maximum yield was obtained at 335 °C. Although the structure of the parent ZrO 2 was retained after recycles, which was confirmed by X-ray diffraction and N 2 adsorption–desorption measurements, the activity of SO 4 2− /ZrO 2 could only be partially recovered by simply calcination. The catalytic activity decrease could be mainly attributed to SO 4 2− leaching, and the activity could be restored by further impregnation of H 2 SO 4 .
研究领域:
化学工程
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生物质能
·
催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2019
·
IF 5.162
Bin Hu,Qiang Lu,Yu-ting Wu,Wen-luan Xie,Min-shu Cui,Ji Liu,Chang-qing Dong,Yong-ping Yang
The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H 3 PO 4 ) offers a promising method for the selective production of levoglucosenone (LGO), a valuable anhydrosugar product. However, the fundamental mechanism for selective LGO formation is unclear. Herein, quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H 3 PO 4 -catalyzed cellulose pyrolysis. H 3 PO 4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways, promoting LGO formation. Through different pathways in the non-catalytic and H 3 PO 4 -catalyzed conditions, LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan. The major catalytic formation pathways of LGO comprise similar reactions, with dehydration at the 3-OH + 2-H site as the rate-determining step. Importantly, secondary conversion of 1,4;3,6-dianhydro-α- d -glucopyranose is not feasible for LGO formation, in contrast to previous reports. In addition, a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process, because the glycosidic bond is important for the formation of the bicyclic structure (1,5- and 1,6-acetal rings).
研究领域:
化学工程
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生物质能
·
量子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2022
·
IF 6.437
Bo Wang,Kai Li,Dong-hong Nan,Shi-yu Feng,Bin Hu,Ti-peng Wang,Qiang Lu
A new method was developed for the selective production of levoglucosenone (LGO) from catalytic pyrolysis of waste paper. Copy paper (CP) was selected as the representative waste paper and subjected to single or combined pretreatment with ethanol and HCl solutions. The influences of pretreatment method, acid concentration, and pretreatment temperature were systematically investigated to reveal their impacts on the physicochemical properties and pyrolytic characteristics of CP as well as LGO formation. The catalytic pyrolysis experiments of pretreated CP were conducted using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and lab-scale device under different pyrolysis temperatures and sample/catalyst ratios. The results showed that the combined ethanol-HCl pretreatment was the most conducive to LGO production, with the optimal pretreatment conditions of acid concentration of 23% and pretreatment temperature of 80 °C. With phosphoric acid-activated carbon (PAC) as the catalyst, the maximum yields of LGO reached 18.15 wt% and 14.76 wt% at 260 °C from Py-GC/MS and lab-scale experiments with sample/catalyst ratios of 4 and 5, respectively. Compared with cellulose and biomass materials, catalytic pyrolysis of pretreated CP had the advantages of high LGO yield and low production temperature.
研究领域:
生物质能
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化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Anbang Xu,Xin Huang,Guangchuan Tang,Lei Tang,Changlei Qin,Zhongqing Yang,Jingyu Ran
Levoglucosenone (LGO) has shown a promising potential in the application of the sustainable chemistry. In this work, alkali metal-doped phosphotungstic acids, M 2.5 H 0.5 PW 12 O 40 (M = Li, Na, K, Rb and Cs), were synthesized and employed for catalytic fast pyrolysis of cellulose to selectively produce LGO. The results show that levoglucosan , the main precursor of LGO, was produced with a yield of 33.5 wt% by non-catalytic pyrolysis of cellulose, while LGO by catalytic fast pyrolysis of cellulose is mainly regulated by the strong/weak acid sites of the M 2.5 H 0.5 PW 12 O 40 . Increasing the atomic radius of the alkali metals from Li to Cs doping to phosphotungstic acid led to an increase of LGO yield, attaining to 15.6 wt% at 300 °C over Cs 2.5 H 0.5 PW 12 O 40 due to a high strong/weak acid site ratio. In addition, LGO yield was further enhanced to 19.2 wt% over (NH 4 ) 2 HPO 4 modified Cs 2.5 H 0.5 PW 12 O 40 as a result of an increase of moderate strong acid sites. This study provides a potential method for LGO production by catalytic pyrolysis of cellulose.
研究领域:
化学工程
·
可再生资源利用
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Bo Wang,Kai Li,Cheng-bo Zhang,Ting Huang,Ti-peng Wang,Qiang Lu
A series of regenerated cellulose (RC) were prepared by a H 3 PO 4 -H 2 O system with different H 3 PO 4 concentrations. The effects of H 3 PO 4 concentrations on the physicochemical properties of RCs were studied, including crystallinity index (CrI), hydrogen bond energy (E H ), accessibility, and degree of polymerization (DP). The catalytic pyrolysis experiments of RCs were executed with a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) instrument and a lab-scale device, to investigate the regulatory function of cellulose structure on the LGO formation. The results indicated that the H 3 PO 4 -H 2 O system could transform the cellulose crystal form from Ⅰ to amorphous form, reduce its CrI and E H significantly, improve its accessibility, while had slight effects on the DP. These changes made RC more appropriate for the selective preparation of LGO, and the corresponding optimal catalyst loading and pyrolytic temperature were also decreased significantly. With phosphoric acid activated carbon as the catalyst, the highest yield of LGO from RC in Py-GC/MS experiments reached 21.50 wt% at catalyst/cellulose (Cat/Cel) ratio of 1/5 and 270 °C, which was much higher than the 18.16 wt% of LGO gained from untreated cellulose at Cat/Cel ratio of 1/3 and 300 °C. In the lab-scale device, the maximum LGO yield from RC was 17.09 wt% at 270 °C and Cat/Cel ratio of 1/6.
研究领域:
生物质能
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Shi-Yu Feng,Sheng Li,Wan-Zhao Huang,Qi Niu,Deng-Yu Chen,Zhi-Mo Fang,Li-Juan Gao,Kai Li,Qiang Lu
With the increasing demand for cellulose acetate (CA) in industrial and daily applications, the disposal of its waste has emerged as an environmental concern. In this study, a novel and sustainable method for value-added utilization of waste CA was proposed, which involved NaOH pretreatment and subsequent catalytic pyrolysis using phosphoric acid-activated carbon (PAC) to prepare levoglucosone (LGO). The effects of pretreatment temperatures and NaOH concentrations on the physicochemical characteristics of CA were thoroughly investigated. Furthermore, the pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were conducted to methodically assess the impacts of both pretreatment and pyrolysis conditions on the production of LGO. The results indicated that NaOH pretreatment could effectively hydrolyze the ester bonds in CA, leading to the removal of acetyl groups and a decrease in thermal stability. At a pretreatment temperature of 40 °C, a NaOH concentration of 0.5 mol/L, a catalyst/sample ratio of 1/3, and a pyrolysis temperature of 400 °C, the LGO yield could reach 11.52 wt%, much higher than that obtained from catalytic pyrolysis of CA (2.70 wt%). This study provides an efficient method for treating waste CA and demonstrates its potential for conversion into high-value chemicals, laying a solid foundation for the green recycling of waste plastics.
研究领域:
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2014
·
IF 3.07
Xinlai Wei,Zhi Wang,Yang Wu,Zhimin Yu,Jie Jin,Ke Wu
Various metal oxides, such as zirconia, titania, and alumina, were screened as solid acid catalysts in the fast pyrolysis of cellulose for levoglucosenone production. The liquid yields were affected by the properties of the catalyst, and an increase in levoglucosenone was observed with the addition of mesoporous metal oxides. Good catalytic properties were observed for anatase titanium oxide with an optimum surface area and pore diameter resulting in a levoglucosenone yield that was as much as 4.98%. The activities of calcined sulfated zirconia increased substantially compared to zirconia-impregnated sulfuric acid without calcination. In the presence of solid super-acid SO 4 2− /ZrO 2 , cellulose produced levoglucosenone in a 7.25% yield.
研究领域:
化学工程
·
生物质能
·
催化科学
✓ 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）