A new kind of multiple metal (Cu, Mg, Ce) doped Ni based mixed oxide catalyst, synthesized by the co-precipitation method, was used for efficient production of hydrogen from bio-oil reforming at 250-500℃. Two refor...A new kind of multiple metal (Cu, Mg, Ce) doped Ni based mixed oxide catalyst, synthesized by the co-precipitation method, was used for efficient production of hydrogen from bio-oil reforming at 250-500℃. Two reforming processes, the conventional steam reforming (CSR) and the electrochemical catalytic reforming (ECR), were performed for the bio-oil reforming. The catalyst with an atomic mol ratio of Ni:Cu:Mg:Ce:AI=5.6:1.1:1.9:1.0:9.9 exhibited very high reforming activity both in CSR and ECR processes, reaching 82.8% hydrogen yield at 500℃ in the CSR, yield of 91.1% at 400℃ and 3.1 A in the ECR, respectively. The influences of reforming temperature and the current through the catalyst in the ECR were investigated. It was observed that the reforming and decomposition of the bio-oil were significantly enhanced by the current. The promoting effects of current on the decomposition and reforming processes of bio-oil were further studied by using the model compounds of bio- oil (acetic acid and ethanol) under 101 kPa or low pressure (0.1 Pa) through the time of flight analysis. The catalyst also shows high water gas shift activity in the range of 300-600 ℃. The catalyst features and alterations in the bio-oil reforming were characterized by the ICP, XRD, XPS and BET measurements. The mechanism of bio-oil reforming was discussed based on the study of the elemental reactions and catalyst characterizations. The research catalyst, potentially, may be a practical catalyst for high efficient production of hydrogen from reforming of bio-oil at mild-temperature.展开更多
A lab-scale fluidized bed is setup and pyrolysis experiments are carried out. When temperature ranges from 400 to 700 ℃, the yields of solid residue, bio-oil and syngas range from 36% to 18%, 19% to 30% and 9% to 42%...A lab-scale fluidized bed is setup and pyrolysis experiments are carried out. When temperature ranges from 400 to 700 ℃, the yields of solid residue, bio-oil and syngas range from 36% to 18%, 19% to 30% and 9% to 42%, respectively, and the mass balance of pyrolysis ranges from 80% to 95%. At 400 to 700 ℃, the characteristics of bio-oil are similar and the heat value is about 10 MJ/kg. When the temperature is over 600℃, the yield of syngas increases approximately twice as much as that at 500 ℃. The yields of CO2 and CO increase from 70 to 230 L/kg and 50 to 106 L/kg, respectively, while the yield of syngas only increases about 5% when the temperature increases from 600 to 700 ℃. The results indicate that the pyrolysis mechanism of waste paper is similar from 400 to 700 ℃, while the yield of syngas can be affected by secondary pyrolysis of bio-oil.展开更多
[Objective] This study was to explore the effect of three precursors on the accumulation of principal volatile oil constituents in tissue culture plantlets of Atractylodes lancea (Thunb.) DC. with the aim to provide...[Objective] This study was to explore the effect of three precursors on the accumulation of principal volatile oil constituents in tissue culture plantlets of Atractylodes lancea (Thunb.) DC. with the aim to provide references for the improvement of artificial cultivated A. lancea quality. [Method] Three precursors were added into the MS rooting medium for A. lancea tissue culture plantlets and the volatile oil was extracted by ultrasonication after cultured for several days. The content of atractylon, atractylol, β-eucalyptol and atractydin in the volatile oil were determined by using gas chromatography method. [Result] The addition of xylose, isoprene and tetrahydrofuran impacted the growth indicators, yield of volatile oil and relative percentage content of the four constituents of A. lancea tissue culture plantlets. In the 6 g/L xylose optimized medium, the atractylon and β-eucalyptol content reached up to 4.23% and 56.34%, respectively, 1.41% and 1.66% higher than the control; although the addition of isoprene into medium raised the atractylon content, the accumulation of total volatile oil was inhibited that it decreased by 23.67%, 31.06% and 7.10% to the control; for the tetrahydrofuran optimized medium, the content of atractylon, atractylol and atractydin all increased, and the total volatile oil content increased by 49.97% to the control when the concentration of tetrahydrofuran was 0.07 g/L. [Conclusion] The addition of xylose and tetrahydrofuran promoted the accumulation of principal constituents of the volatile oil, whereas the addition of isoprene inhibited the accumulation.展开更多
Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light ...Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil). The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.展开更多
An iterative optimization strategy is proposed and applied to the steady state optimizing control of the bio-dissimilation process of glycerol to 1,3-propanediol in the presence of model-plant mismatch and input const...An iterative optimization strategy is proposed and applied to the steady state optimizing control of the bio-dissimilation process of glycerol to 1,3-propanediol in the presence of model-plant mismatch and input constraints. The scheme is based on the Augmented Integrated System Optimization and Parameter Estimation (AI- SOPE) technique, but a linearization of some performance function in the modified model-based optimization problem of AISOPE is introduced to overcome the difficulty of determining an appropriate penalty parameter. When carrying out the iterative optimization, the penalty coefficient is set to a larger value at the current iteration than at the previous iteration, which can promote the evolution rate of the iterative optimization. Simulation studies illustrate the potential ofthe approach presented for the optimizing control of the bioTdissimilation process of glycerol to 1,3-propanediol. The effects of measurement noise, measured and unmeasured disturbances on the proposed algorithm are also investigated.展开更多
The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compounds in straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with ...The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compounds in straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with a sulfur chemiluminescence detector to harvest a satisfactory result. The identification of the structure of sulfur compounds by comprehensive two-dimensional gas chromatography coupled with the time-of-flight mass spectrometry indicated that cyclo-sulfides, benzothiophenes, dibenzothiophenes, dihydro-benzothiophenes and tetrahydro-dibenzothiophenes were included in straightrun diesel obtained from the Arab medium crude(AM). A total of 259 individual compounds were detected and their molecular structures were identified. The analytical method was approved as an effective way to characterize the composition of sulfur compounds, which reduced the interference of other compounds, facilitated the data presentation and provided more detailed information about molecular composition of sulfur compounds.展开更多
We undertook a pyrolysis research on garlic stalks to solve its difficulty in use. We found that the inorganic salts in biomass played an important role in catalytic pyrolysis. Moreover, we studied the pyrolysis behav...We undertook a pyrolysis research on garlic stalks to solve its difficulty in use. We found that the inorganic salts in biomass played an important role in catalytic pyrolysis. Moreover, we studied the pyrolysis behavior under catalyst and catalyst-free conditions. The results showed that the weightlessness rate of garlic stalks was the highest at 550 ℃ under catalyst-free condition. The oil production rate increased with the increase of temperature and reached the peak at 550 ℃. Subsequently, as the temperature increased, the secondary cracking was intensified and oil production rate was decreased. The oil production rate increased significantly (almost 15%) under catalysis of KOH. However, the oil production rate was the highest at 500-600℃. What's more, we found that KOH played a major role in promoting decomposition of surface skin cells and subcutaneous fibrous layer of garlic stalks.展开更多
Production of benzene, toluene and xylenes (BTX) from bio-oil can provide basic feedstocks for the petrochemical industry. Catalytic conversion of bio-oil into BTX was performed by using different pore characteristi...Production of benzene, toluene and xylenes (BTX) from bio-oil can provide basic feedstocks for the petrochemical industry. Catalytic conversion of bio-oil into BTX was performed by using different pore characteristics zeolites (HZSM-5, HY-zeolite, and MCM-41). Based on the yield and selectivity of BTX, the production of aromatics decreases in the following order: HZSM-5〉MCM-41〉HY-zeolite. The highest BTX yield from bio-oil using HZSM-5 reached 33.1% with aromatics selectivity of 86.4%. The reaction conditions and catalyst characterization were investigated in detail to make clear the optimal operating parameters and the relation between the catalyst structure and the production of BTX.展开更多
Anovel solid acid catalyst, which was prepared from sodium alginate (SA) and metal chlorides and characterized with XRD and FT-IR spectrometry, was used for the preparation of biodiesel via esterification reaction. Th...Anovel solid acid catalyst, which was prepared from sodium alginate (SA) and metal chlorides and characterized with XRD and FT-IR spectrometry, was used for the preparation of biodiesel via esterification reaction. The study results showed that the aluminum-alginate complex prepared in a cheap and easy way exhibited high catalytic activity, and a 92.6% conversion of methyl oleate was obtained in the presence of 4m% of catalyst dosage upon refluxing for 3h of methanol and acid mixed in a molar ratio of 10:1. It should be noted that the catalyst can be applied to the esterification reaction of fatty acids with various carbon chain length on methanol or different short chain alcohols, indicating that the catalyst is suitable for the preparation of biodiesel from waste oils with a high acid value.展开更多
High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products ...High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products distribution were investigated. Both the hydrogen yield and carbon conversion were remarkably enhanced by the current through the catalyst, reaching hydrogen yield of 70% and carbon conversion of 85% at a lower reforming temperature of 500 ℃. The influence of current on the properties of the CoZnAl catalyst was also characterized by X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and Brunauer-Emmett-Teller measurements. The thermal electrons would play an important role in promoting the reforming reactions of the oxygenated-organic compounds in the bio-oil.展开更多
文摘A new kind of multiple metal (Cu, Mg, Ce) doped Ni based mixed oxide catalyst, synthesized by the co-precipitation method, was used for efficient production of hydrogen from bio-oil reforming at 250-500℃. Two reforming processes, the conventional steam reforming (CSR) and the electrochemical catalytic reforming (ECR), were performed for the bio-oil reforming. The catalyst with an atomic mol ratio of Ni:Cu:Mg:Ce:AI=5.6:1.1:1.9:1.0:9.9 exhibited very high reforming activity both in CSR and ECR processes, reaching 82.8% hydrogen yield at 500℃ in the CSR, yield of 91.1% at 400℃ and 3.1 A in the ECR, respectively. The influences of reforming temperature and the current through the catalyst in the ECR were investigated. It was observed that the reforming and decomposition of the bio-oil were significantly enhanced by the current. The promoting effects of current on the decomposition and reforming processes of bio-oil were further studied by using the model compounds of bio- oil (acetic acid and ethanol) under 101 kPa or low pressure (0.1 Pa) through the time of flight analysis. The catalyst also shows high water gas shift activity in the range of 300-600 ℃. The catalyst features and alterations in the bio-oil reforming were characterized by the ICP, XRD, XPS and BET measurements. The mechanism of bio-oil reforming was discussed based on the study of the elemental reactions and catalyst characterizations. The research catalyst, potentially, may be a practical catalyst for high efficient production of hydrogen from reforming of bio-oil at mild-temperature.
基金The National High Technology Research and Devel-opment Program of China (863Program)(No2006AA020101)the National Basic Research Program of China (973Program) ( No2005CB221202)the Open Foundation of State Key Laboratory of CleanEnergy Utilization of Zhejiang University (NoZJUCEU2006004)
文摘A lab-scale fluidized bed is setup and pyrolysis experiments are carried out. When temperature ranges from 400 to 700 ℃, the yields of solid residue, bio-oil and syngas range from 36% to 18%, 19% to 30% and 9% to 42%, respectively, and the mass balance of pyrolysis ranges from 80% to 95%. At 400 to 700 ℃, the characteristics of bio-oil are similar and the heat value is about 10 MJ/kg. When the temperature is over 600℃, the yield of syngas increases approximately twice as much as that at 500 ℃. The yields of CO2 and CO increase from 70 to 230 L/kg and 50 to 106 L/kg, respectively, while the yield of syngas only increases about 5% when the temperature increases from 600 to 700 ℃. The results indicate that the pyrolysis mechanism of waste paper is similar from 400 to 700 ℃, while the yield of syngas can be affected by secondary pyrolysis of bio-oil.
基金Supported by the National Natural Science Foundation of China(31070443)the National Science Foundation of China for Talent Training in Basic Research(J1103507)+1 种基金The Priority Academic Program Development of Jiangsu Higher Education Institutions,Innovation Promotion Project of Nanjing Municipal Science and Technology Commissions(201105058)the Practice and Innovation Training Program for the Students of Nanjing Normal University~~
文摘[Objective] This study was to explore the effect of three precursors on the accumulation of principal volatile oil constituents in tissue culture plantlets of Atractylodes lancea (Thunb.) DC. with the aim to provide references for the improvement of artificial cultivated A. lancea quality. [Method] Three precursors were added into the MS rooting medium for A. lancea tissue culture plantlets and the volatile oil was extracted by ultrasonication after cultured for several days. The content of atractylon, atractylol, β-eucalyptol and atractydin in the volatile oil were determined by using gas chromatography method. [Result] The addition of xylose, isoprene and tetrahydrofuran impacted the growth indicators, yield of volatile oil and relative percentage content of the four constituents of A. lancea tissue culture plantlets. In the 6 g/L xylose optimized medium, the atractylon and β-eucalyptol content reached up to 4.23% and 56.34%, respectively, 1.41% and 1.66% higher than the control; although the addition of isoprene into medium raised the atractylon content, the accumulation of total volatile oil was inhibited that it decreased by 23.67%, 31.06% and 7.10% to the control; for the tetrahydrofuran optimized medium, the content of atractylon, atractylol and atractydin all increased, and the total volatile oil content increased by 49.97% to the control when the concentration of tetrahydrofuran was 0.07 g/L. [Conclusion] The addition of xylose and tetrahydrofuran promoted the accumulation of principal constituents of the volatile oil, whereas the addition of isoprene inhibited the accumulation.
基金This work is supported by the National Key Basic Program of China (No.2013CB228105) and the National Natural Science Foundation of China (No.51161140331).
文摘Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil). The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.
基金the State Science and Technology Project of China (No.2001BA204B01).
文摘An iterative optimization strategy is proposed and applied to the steady state optimizing control of the bio-dissimilation process of glycerol to 1,3-propanediol in the presence of model-plant mismatch and input constraints. The scheme is based on the Augmented Integrated System Optimization and Parameter Estimation (AI- SOPE) technique, but a linearization of some performance function in the modified model-based optimization problem of AISOPE is introduced to overcome the difficulty of determining an appropriate penalty parameter. When carrying out the iterative optimization, the penalty coefficient is set to a larger value at the current iteration than at the previous iteration, which can promote the evolution rate of the iterative optimization. Simulation studies illustrate the potential ofthe approach presented for the optimizing control of the bioTdissimilation process of glycerol to 1,3-propanediol. The effects of measurement noise, measured and unmeasured disturbances on the proposed algorithm are also investigated.
基金financially supported by the National Basic Research Program of China (973 Program) (2012CB224800)
文摘The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compounds in straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with a sulfur chemiluminescence detector to harvest a satisfactory result. The identification of the structure of sulfur compounds by comprehensive two-dimensional gas chromatography coupled with the time-of-flight mass spectrometry indicated that cyclo-sulfides, benzothiophenes, dibenzothiophenes, dihydro-benzothiophenes and tetrahydro-dibenzothiophenes were included in straightrun diesel obtained from the Arab medium crude(AM). A total of 259 individual compounds were detected and their molecular structures were identified. The analytical method was approved as an effective way to characterize the composition of sulfur compounds, which reduced the interference of other compounds, facilitated the data presentation and provided more detailed information about molecular composition of sulfur compounds.
基金Supported by National Major Water Project of Eleventh Five-Year Plan(2008ZX07105002)~~
文摘We undertook a pyrolysis research on garlic stalks to solve its difficulty in use. We found that the inorganic salts in biomass played an important role in catalytic pyrolysis. Moreover, we studied the pyrolysis behavior under catalyst and catalyst-free conditions. The results showed that the weightlessness rate of garlic stalks was the highest at 550 ℃ under catalyst-free condition. The oil production rate increased with the increase of temperature and reached the peak at 550 ℃. Subsequently, as the temperature increased, the secondary cracking was intensified and oil production rate was decreased. The oil production rate increased significantly (almost 15%) under catalysis of KOH. However, the oil production rate was the highest at 500-600℃. What's more, we found that KOH played a major role in promoting decomposition of surface skin cells and subcutaneous fibrous layer of garlic stalks.
文摘Production of benzene, toluene and xylenes (BTX) from bio-oil can provide basic feedstocks for the petrochemical industry. Catalytic conversion of bio-oil into BTX was performed by using different pore characteristics zeolites (HZSM-5, HY-zeolite, and MCM-41). Based on the yield and selectivity of BTX, the production of aromatics decreases in the following order: HZSM-5〉MCM-41〉HY-zeolite. The highest BTX yield from bio-oil using HZSM-5 reached 33.1% with aromatics selectivity of 86.4%. The reaction conditions and catalyst characterization were investigated in detail to make clear the optimal operating parameters and the relation between the catalyst structure and the production of BTX.
基金financially supported by the International Science & Technology Cooperation Program of China(No.2010DFB60840)the Key Science and Technology Project of Guizhou Province(No.20076004)+1 种基金the Social Development S&T Program(No.SZ-[2009]3011)the National Key Technology R&D Program(No.2006BAD07A12)
文摘Anovel solid acid catalyst, which was prepared from sodium alginate (SA) and metal chlorides and characterized with XRD and FT-IR spectrometry, was used for the preparation of biodiesel via esterification reaction. The study results showed that the aluminum-alginate complex prepared in a cheap and easy way exhibited high catalytic activity, and a 92.6% conversion of methyl oleate was obtained in the presence of 4m% of catalyst dosage upon refluxing for 3h of methanol and acid mixed in a molar ratio of 10:1. It should be noted that the catalyst can be applied to the esterification reaction of fatty acids with various carbon chain length on methanol or different short chain alcohols, indicating that the catalyst is suitable for the preparation of biodiesel from waste oils with a high acid value.
基金ACKNOWLEDGMENTS This work was supported by the National Basic Research Program of Ministry of Science and Technology of China (No.2007CB210206), the National High Technology Research and Development Program (No.2009AA05Z435), the National Natural Science Foundation of China (No.50772107), and the Demonstration and Applied Investigation of Biomass Clean Energy Base (No.2007-15).
文摘High-efficient production of hydrogen from bio-oil was performed by electrochemical catalytic reforming method over the CoZnAl catalyst. The influence of current on the hydrogen yield, carbon conversion, and products distribution were investigated. Both the hydrogen yield and carbon conversion were remarkably enhanced by the current through the catalyst, reaching hydrogen yield of 70% and carbon conversion of 85% at a lower reforming temperature of 500 ℃. The influence of current on the properties of the CoZnAl catalyst was also characterized by X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis, and Brunauer-Emmett-Teller measurements. The thermal electrons would play an important role in promoting the reforming reactions of the oxygenated-organic compounds in the bio-oil.