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1.
Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 °C with N2 as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N2, particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 °C) and 2 L/min of N2 flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques.  相似文献   

2.
Spent K-Cups were liquefied into crude bio-oil in a water-ethanol co-solvent mixture and reaction conditions were optimized using response surface methodology (RSM) with a central composite design (CCD). The effects of three independent variables on the yield of crude bio-oil were examined, including the reaction temperature (varied from 255 °C to 350 °C), reaction time (varied from 0 min to 25 min) and solvent/feedstock mass ratio (varied from 2:1 to 12:1). The optimum reaction conditions identified were 276 °C, 3 min, and solvent/feedstock mass ratio of 11:1, giving a mass fraction yield of crude bio-oil of 60.0%. The overall carbon recovery at the optimum conditions was 93% in mass fraction. The effects of catalyst addition (NaOH and H2SO4) on the yield of crude bio-oil were also investigated under the optimized reaction conditions. The results revealed that the presence of NaOH promoted the decomposition of feedstock and significantly enhanced the bio-oil production and liquefaction efficiency, whereas the addition of H2SO4 resulted in a negative impact on the liquefaction process, decreasing the yield of crude bio-oil.  相似文献   

3.
Spent coffee grounds (SCG) were liquefied in hot-compressed water to produce crude bio-oil via hydrothermal liquefaction (HTL) in a 100 cm3 stainless-steel autoclave reactor in N2 atmosphere. We investigated the effects of operating parameters such as retention times (5 min, 10 min, 15 min, 20 min and 25 min), reaction temperatures (200 °C, 225 °C, 250 °C, 275 °C and 300 °C), and water/feedstock mass ratios (5:1, 10:1, 15:1 and 20:1) and initial pressure of process gas (2.0 MPa and 0.5 MPa) on the yield and properties of the resulting crude bio-oil. The highest yield of the crude bio-oil (47.3% mass fraction) was obtained at conditions of 275 °C, 10 min retention time and water/feedstock mass ratio of 20:1 with an initial pressure of 2.0 MPa. The elemental analysis of the produced crude bio-oil revealed that the oil product had a higher heating value (HHV) of 31.0 MJ kg−1, much higher than that of the raw material (20.2 MJ kg−1). GC–MS and FT-IR measurements showed that the main volatile compounds in the crude bio-oil were long chain aliphatic acids and esters.  相似文献   

4.
The black cumin seed cake (BCSC) is a by-product obtained from the black cumin seeds with cold pressing. This by-product can be utilized as a biomass feedstock for conversion to bio-oil with pyrolysis process. The BCSC samples were initially pyrolyzed on a lab-scale pyrolysis system at different values in the ranges of 300-800 °C and 0.050-0.300 L min−1 to determine the effects of operation temperature and N2 flow rate on the yields on products, respectively. Then, the bio-oil in the highest yield (wB = 44.37%) which was obtained at pyrolysis final temperature (450 °C) temperature, heating rate (35 °C min−1), particle size (dp > 850 ??m), and sweeping flow rate of 0.200 L min−1 was characterized by Fourier Transform infra-red (FT-IR) spectroscopy, gas chromatography/mass spectrometry (GC-MS) and column chromatography. Consequently, it was shown that the operating temperature and N2 gas flow rate parameters were effective on the product yields. Also, the important some physico-chemical properties of the pyrolytic oil obtained in high yield were determined as the calorific value of 38.48 MJ kg−1, the empirical formula of CH1.651O0.105N0.042S0.001, the rich chemical content containing many different chemical groups, and the density of 970.25 kg m−3, and the viscosity of 63.42 mm2 s−1. Based on the determined properties of the pyrolytic oil, it was decided that the use of pyrolytic oil derived from the BCSC may possible be for the production of the alternative liquid fuels and finely chemicals after the necessary improvements.  相似文献   

5.
Rice straw as a bio-oil source via pyrolysis and steam pyrolysis   总被引:3,自引:0,他引:3  
The pyrolysis of rice straw was studied to estimate the effect of pyrolysis conditions on product yields and bio-oil composition when the heating rate was 5 K/min. Pyrolysis temperature, particle size, sweeping gas flow rate and steam velocity were the experimental parameters. Among the four pyrolysis temperatures; namely, 673, 773, 823 and 973 K; 823 K gave the highest bio-oil yield of 27.26%. Six different particle sizes were examined and sample having a particle size of 0.425<Dp<0.85 mm had a bio-oil yield of 27.77%. Nitrogen was used as the sweeping gas with the flow rates of either 50, 100, 200 and 400 ml/min and the highest bio-oil yield was obtained when flow rate was 200 ml/min. The bio-oil yield reached a maximum value of 35.86% with the steam velocity of 2.7 cm/s. Liquid products obtained from pyrolysis, inert atmosphere pyrolysis and steam pyrolysis were then fractionated into aspalthanes and maltanes. The aliphatic subfraction obtained by column chromatography was then analysed by GC/MS. For further structural analysis, the pyrolysis oils were conducted with 1H-NMR, oils and aliphatic subfractions with FT-IR. The chemical characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks.  相似文献   

6.
Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H2 yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H2-TPD and the N2 adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.  相似文献   

7.
Hydrogen produced from renewable resources is becoming interesting as an alternative to conventional fossil fuels. Co-based catalysts have been reported for their active role in steam reforming of acetic acid as the main model compound of bio-oil aqueous fraction. In the present work, a series of Co–Cr/SBA-15 extrudates were prepared by varying the binder (bentonite) content and particle size in order to get catalyst particles suitable to be used in a steam reformer at industrial scale. Catalysts were characterized by N2 physisorption, ICP-AES, TEM, SEM, XRD and H2-TPR. The physicochemical characterization results showed that no remarkable changes occurs after the extruding process of the powdered sample, except for the particle size and mechanical strength. Acetic acid steam reforming tests were done at 600 °C and WHSV = 30.1 h−1 varying the feed flow rate and the catalysts particle size in order to study the influence of internal and external diffusion limitations. Extruded particles with an effective diameter of 1.5 mm and 30 wt% of bentonite get similar conversion and hydrogen selectivity than powder sample. Besides, the agglomerated catalysts are also stable up to 12 h of TOS.  相似文献   

8.
A novel process for hydrogen production via bio-oil catalytic reforming without steam addition was proposed. The liquid feedstock was a distillation fraction from crude bio-oil molecular distillation. The fraction obtained was enriched with the low-molecular-weight organics (acids, aldehydes, and ketones), and contained nearly all of the water from crude bio-oil. The highest catalytic performance, with a carbon conversion of 95% and a H2 yield of 135 mg g−1 organics, was obtained by processing the distillate over Ni/Al2O3 catalyst at 700 °C. The steam involved in the reforming reaction was derived entirely from the water in the crude bio-oil. The fresh and spent catalysts were characterized by N2-physisorption, thermogravimetric analysis, and high-resolution transmission electron microscopy. To further understand the reaction mechanisms, symmetric density functional theory calculations for decomposition were performed on four model compounds in bio-oil (acetic acid, hydroxyacetone, furfural, and phenol) over the Ni(111) surface. In addition, the decomposition of H2O∗ to OH∗ and O∗ and their subsequent steam reforming reactions with carbon precursors (CH∗ and CH3C∗) were also examined.  相似文献   

9.
Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, QD/H2 (kJ/Nm3) and YBio-oil/H2 (kg/Nm3)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the YBio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the QD/H2 was slightly increased, just by 7.55%.  相似文献   

10.
Chemical looping steam reforming of bio-oil is novel conversion technology utilizing waste energy, which is an advantage to reduce cost and improve environmental. However, complex reaction process between oxygen carrier and bio-oil constrain its development. In this study, perovskite based La0.8M0.2Ni0.8Fe0.2O3 (M = Ca, Ce and Zr) were investigated as an oxygen carrier for chemical looping steam reforming of bio-oil model reaction. The perovskites were prepared via sol-gel method and the effect of doping for reforming of acetic acid as bio-oil model compound is also investigated. Among all the perovskite tested, Ce doped La0.8Ce0.2Ni0.8Fe0.2O3 oxygen carrier gave superior and stable catalytic performance for 1440 min at 600 °C and steam/carbon mole ratio (S/C = 2). The fresh and spent oxygen carriers were characterized using XRD, H2-TPR, CO2-TPD, TG-DTG, Dielectric constant, Raman, XPS and XANES. Doping with base metal generally, improved coke resistance ability of the perovskite. CO2-TPD and XPS analysis reveal that the highest carbon resistance for La0.8Ce0.2Ni0.8Fe0.2O3 perovskite is due to enhanced stronger surface basicity and oxygen adsorption. From DFT simulation and Dielectric constant results, the better activity for La0.8Ce0.2Ni0.8Fe0.2O3 is attributed to its adsorption ability of reactants, oxygen and electron transfer from sub-surface to surface of the perovskite.  相似文献   

11.
Hydrogen production was studied in the catalytic steam reforming of a synthetic and a real aqueous fraction of bio-oil. Ni/Al coprecipitated catalysts with varying nickel content (23, 28 and 33 relative atomic %) were prepared by an increasing pH technique and tested during 2 h under different experimental conditions in a small bench scale fixed bed setup. The 28% Ni catalyst yielded a more stable performance over time (steam-to-carbon molar ratio, S/C = 5.58) at 650 °C and a catalyst weight/organic flow rate (W/morg) ratio of 1.7 g catalyst min/g organic. Using the synthetic aqueous fraction as feed, almost complete overall carbon conversion to gas and hydrogen yields close to equilibrium could be obtained with the 28% Ni catalyst throughout. Up to 63% of overall carbon conversion to gas and an overall hydrogen yield of 0.09 g/g organic could be achieved when using the real aqueous fraction of bio-oil, but the catalyst performance showed a decay with time after 20 min of reaction due to severe coke deposition. Increasing the W/morg ratio up to 5 g catalyst min/g organic yielded a more stable catalyst performance throughout, but overall carbon conversion to gas did not surpass 83% and the overall hydrogen yield was only ca. 77% of the thermodynamic equilibrium. Increasing reaction temperatures (600–800 °C) up to 750 °C enhanced the overall carbon conversion to gas and the overall yield to hydrogen. However, at 800 °C the catalyst performance was slightly worse, as a result of an increase in thermal cracking reactions leading to an increased formation of carbon deposits.  相似文献   

12.
High efficient production of lower alcohols (C1–C5 mixed alcohols) from hydrogen rich bio-oil derived syngas was achieved in this work. A non-catalytic partial oxidation (NPOX) gasification technology was successfully applied in the production and conditioning of bio-oil derived syngas using bio-oil (BO) and emulsifying waste engine oil (EWEO) as feedstock. The effects of water addition and feedstock composition on the gasification performances were investigated. When the BO20 and EWEO30 was mixed with mass ratio of 1: 0.33, the maximum hydrogen yield of 93.7% with carbon conversion of 96.7% was obtained, and the hydrogen rich bio-oil derived syngas was effectively produced. Furthermore, a two-stage bed reactor was applied in the downstream process of lower alcohols synthesis from hydrogen rich bio-oil derived syngas (H2/CO/CO2/CH4/N2 = 52.2/19.5/3.0/9.4/15.9, v/v). The highest carbon conversion of 42.5% and the maximum alcohol yield of 0.18 kg/kgcat h with selectivity of 53.8 wt% were obtained over the Cu/ZnO/Al2O3(2.5)//Cu25Fe22Co3K3/SiO2(2.5) catalyst combination system. The mechanism and evaluation for lower alcohols synthesis from model bio-oil derived syngas and model mixture gas were also discussed. The integrative process of hydrogen rich bio-oil derived syngas production and downstream lower alcohols synthesis, potentially providing a promising route for the conversion of organic wastes into high performance fuels and high value-added chemicals.  相似文献   

13.
Pyrolysis of Xanthium strumarium has been performed in a fixed-bed tubular reactor with boron minerals (ulexite, colemanite, and borax) and without catalyst at three different temperatures ranging from 350°C to 550°C with heating rate of 50°C/min. The amounts of bio-oil, bio-char, and gas generated, also the compositions of the resulting bio-oils were identified by GC-MS and FT-IR. The influences of pyrolysis parameters, such as temperature and catalyst on product yields were investigated. Temperature and catalyst were found to be the main factors affecting the conversion of Xanthium strumarium into solid, liquid, and gaseous products. The highest liquid yield (27.97%) including water was obtained with 10% colemanite (Ca2B6O11.5H2O) catalyst at 550°C temperature at a heating rate of 50°C/min when 0.224 > Dp > 0.150 mm particle size raw material and 100 cm3/min of sweeping gas flow rate were used.  相似文献   

14.
Steam reforming of bio-oil for hydrogen production is a promising green technology. Acetic acid was used as the bio-oil model compound. Experimental and density functional theory calculations were carried out to study the performance of Co/Al2O3 catalysts doped with boron (B) with a 1 wt.%–5 wt.% content. Catalyst characterization by BET, XRD, XPS, NH3-TPD, H2-TPR, TEM, and TG-DTG was performed. We found that the catalyst performance improved significantly by B doping. Under the reaction conditions of T = 500 °C, steam-to-carbon ratio (S/C) = 5, and liquid hourly space velocity (LHSV) = 4.3 h?1, the catalyst with a B doping ratio of 1 wt.% had the highest hydrogen yield of 85% and a maximum acetic acid conversion rate of 95%. The corresponding hydrogen productivity was 0.8 mmol/min. The stability of this catalyst exceeded 29 h. Density functional theory calculations showed that the interactions between the reaction intermediates and the surface were strengthened with B addition.  相似文献   

15.
Zeolite L featuring different size and shape (nanocrystals and discs), with and without alkaline metal exchange (Cs or Na), was used as catalyst support in bio-oil/bio-glycerol mixture Steam Reforming (SR). Zeolites were modified with CeO2 to improve support properties before the impregnation of nickel. Then, prepared catalysts were tested in SR of a multi-component synthetic bio-oil/bio-glycerol mixture at 1073 and 973 K, under atmospheric pressure and using a Steam to Carbon (S/C) ratio of 5.0. Activity tests showed that catalysts deactivated during the experiments at 973 K. In addition, the sodium exchange produced the sintering of the Zeolite L crystals. Thus, Na containing catalysts produced low conversions and hydrogen yields lower than 30%. On the other hand, Cs containing catalysts resulted in slightly lower hydrogen yields than the supports without this metallic cation. Regarding the morphology of the zeolites, the ones with disc shape were the most active for bio-oil SR purposes producing hydrogen yields close to 80% in the first reaction stage at 1073 K and hydrogen yields close to the 50% at the last reaction stage at 1073 K.  相似文献   

16.
Hydrogen production from methane decomposition via an atmospheric pressure rotating gliding arc (RGA) discharge reactor co-driven by a magnetic field and tangential flow is investigated. The motion and V–I characteristics of the RGA are studied with a high-speed camera and oscilloscope. Optical emission spectroscopy (OES) is used to characterize RGA plasmas in N2 and CH4 + N2, and the RGA plasma is shown to occur as a warm plasma. For the CH4 + N2 plasma, CN, C2, and CH spectral lines are observed. The vibrational and rotational temperatures are 0.56–0.86 eV and 1325–1986 K, respectively. The effects of load resistance, the CH4/N2 ratio, and the feed flow rate on the performance of methane decomposition are investigated. The maximum CH4 conversion rate and H2 selectivity are 91.8% and 80.7% when the CH4/N2 ratio is 0.1 and 0.05, respectively, at a flow rate of 6 L/min. The possible reaction mechanisms of the methane decomposition process are discussed. This study is expected to establish a basis for the further industrial applications of H2 production.  相似文献   

17.
This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 gcatalyst h (gbio-oil)−1. The benefits of incorporating La2O3 to the Ni/α-Al2O3 catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La2O3-αAl2O3 catalyst, at 700 °C and space-time of 0.22 gcatalyst h (gbio-oil)−1. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.  相似文献   

18.
Char derived from cyanobacterial blooms (CDCB), by-product of fast pyrolysis of cyanobacterial blooms from Dianchi Lake (Yunnan Province, China) at a final pyrolysis temperature of 500 °C were used as feedstock material in this study. Steam gasification characteristics of CDCB were investigated in a fixed-bed reactor to evaluate the effect of particle size (below 0.15 mm, 0.15–0.3 mm, 0.3–0.45 mm, 0.45–0.9 mm, 0.9–3 mm) and solid residence time (3, 6, 9, 12, 15 min) on gas yield and composition, and experiments were carried out at bed temperature range of 600–850 °C, steam flow rate of 0.178 g/min. The results showed that solid residence time played an important role on steam gasification process, while particle size presented less effect on gasification process; proper particle size and longer residence time were favorable for dry gas yield and carbon conversion efficiency (CCE). At the same time, higher reaction temperature reduced influence of particle size on gasification process, and smaller particle size required less residence time for reaction completed. Maximum dry gas yield and CCE reached 1.84 Nm3 kg−1 and 98.82%, respectively, achieved at a temperature of 850 °C, flow rate of 0.178 g/min, solid residence time of 15 min and particle size range of 0.45–0.9 mm.  相似文献   

19.
This article presents the effect of metal loading and support modification with MgO on low-temperature steam reforming of ethanol (LTSRE) over Ni–Sn/CeO2 catalysts prepare by a single-pot solution combustion synthesis (SCS) method. Atmospheric pressure activity study of these catalysts (0.5 g) is performed at different temperatures (200–400 °C), H2O:EtOH = 12: 1 mol ratio, and feed flow rate 0.1 ml/min. After 10 h TOS at 400 °C, NiSn(5)/CM12 catalyst with 5 wt.% total metal loading, optimal Sn (Ni:Sn = 14:1), and Ce:Mg = 1:2 mol ratio shows EtOH conversion 100% and H2 selectivity 70% with low coke deposition. Physicochemical characterizations (XRD, Raman, FESEM, TEM, and N2 adsorption-desorption) reveal that addition of MgO in CeO2 and an optimal amount of Sn decrease both Ni and support particle sizes while oxygen storage capacity (OSC) of the support increases (by XPS). Alkaline characteristics of MgO reduces support's acidity and improves active metal-support interaction, as evaluated by NH3-TPD and H2-TPR.  相似文献   

20.
High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo–10Ni/γ-Al2O3 catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo–10Ni/γ-Al2O3 catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC–MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. It is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil.  相似文献   

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