首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 343 毫秒
1.
Biogas plants, increasing in number, produce a stream of fermentation residue with high organic content, providing an energy source which is by now mostly unused. We tested this biomass as a potential feedstock for catalytic gasification in supercritical water (T  374 °C, p  22 MPa) for methane production using a batch reactor system. The coke formation tendency during the heat-up phase was evaluated as well as the cleavage of biomass-bound sulfur with respect to its removal from the process as a salt. We found that sulfur is not sufficiently released from the biomass during heating up to a temperature of 410 °C. Addition of alkali salts improved the liquefaction of fermentation residues with a low content of minerals, probably by buffering the pH. We found a deactivation of the carbon-supported ruthenium catalyst at low catalyst-to-biomass loadings, which we attribute to sulfur poisoning and fouling in accordance with the composition of the fermentation residue. A temperature of 400 °C was found to maximize the methane yield. A residence time dependent biomass to catalyst ratio of 0.45 g g−1 h−1 was found to result in nearly full conversion with the Ru/C catalyst. A Ru/ZrO2 catalyst, tested under similar conditions, was less active.  相似文献   

2.
《Journal of power sources》2002,109(2):494-499
Nickel hydroxide is prepared by neutralizing NiSO4 solution with 4.8 M NaOH, followed by washing the precipitate and treating the slurry hydrothermally at different temperatures. The parameters varied are: initial nickel concentration; effect of presence of sodium ions during hydrothermal treatment; aging time after hydrothermal treatment. The samples so prepared are chemically analyzed and the physical and electrolytic properties such as tap density, percentage weight loss and discharge capacity are determined. On increasing the temperature from 60 to 160 °C, the discharge capacity increases from 52 to 112 mAh g−1. At 200 °C, the discharge capacity decreases to 94 mAh g−1. Allowing the hydroxide precipitate to age after hydrothermal treatment also causes a decrease in discharge capacity. The presence of excess sodium ions during hydrothermal treatment yields nickel hydroxide with a very low discharge capacity. The maximum discharge capacity of 160 mAh g−1 is obtained for nickel hydroxide prepared under the following conditions: nickel concentration 43 g l−1, neutralizing agent sodium hydroxide, time of hydrothermal treatment 2 h, temperature during hydrothermal treatment 160 °C. XRD patterns and FTIR spectra confirm the precipitate to be β-nickel hydroxide. The sample contains 62.89 wt.% Ni with a tap density of 0.96 g cm−3. TG–DTA measurements show a weight loss of 19% with an endothermic peak at 325 °C which corresponds to the decomposition of nickel hydroxide to nickel oxide. The present method of preparing nickel hydroxide through hydrothermal treatment reduces the aging time to 2 h and gives a product with good filtration characteristics.  相似文献   

3.
《Journal of power sources》2006,157(1):104-113
This paper presents a comprehensive study of hydrogen production from sodium borohydride (NaBH4), which is synthesized from sodium tetraborate (Na2B4O7) decomposition, for proton exchange membrane (PEM) fuel cells. For this purpose, Na2B4O7 decomposition reaction at 450–500 °C under hydrogen atmosphere and NaBH4 decomposition reaction at 25–40 °C under atmospheric pressure are selected as a common temperature range in practice, and the inlet molar quantities of Na2B4O7 are chosen from 1 to 6 mol with 0.5 mol interval as well. In order to form NaBH4 solution with 7.5 wt.% NaBH4, 1 wt.% NaOH, 91.5 wt.% H2O, the molar quantities of NaBH4 are determined. For a PEM fuel cell operation, the required hydrogen production rates are estimated depending on 60, 65, 70 and 75 g of catalyst used in the NaBH4 solution at 25, 32.5 and 40 °C, respectively. It is concluded that the highest rate of hydrogen production per unit area from NaBH4 solution at 40 °C is found to be 3.834 × 10−5 g H2 s−1 cm−2 for 75 g catalyst. Utilizing 80% of this hydrogen production, the maximum amounts of power generation from a PEM fuel cell per unit area at 80 °C under 5 atm are estimated as 1.121 W cm−2 for 0.016 cm by utilizing hydrogen from 75 g catalyst assisted NaBH4 solution at 40 °C.  相似文献   

4.
《Journal of power sources》2006,155(2):340-352
Thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the combined processes of dimethyl ether (DME) partial oxidation and steam reforming were investigated as a function of oxygen-to-carbon ratio (0.00–2.80), steam-to-carbon ratio (0.00–4.00), temperature (100 °C–600 °C), pressure (1–5 atm) and product species.Thermodynamically, dimethyl ether processed with air and steam generates hydrogen-rich fuel-cell feeds; however, the hydrogen concentration is less than that for pure DME steam reforming. Results of the thermodynamic processing of dimethyl ether indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 °C, oxygen-to-carbon ratios greater than 0.00 and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure has negligible effects on the hydrogen content. Thermodynamically, dimethyl ether can produce concentrations of hydrogen and carbon monoxide of 52% and 2.2%, respectively, at a temperature of 300 °C, and oxygen-to-carbon ratio of 0.40, a pressure of 1 atm and a steam-to-carbon ratio of 1.50. The order of thermodynamically stable products (excluding H2, CO, CO2, DME, NH3 and H2O) in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol and methyl-ethyl ether; trace amounts of formaldehyde, formic acid and methanol are observed.Ammonia and hydrogen cyanide are also thermodynamically favored products. Ammonia is favored at low temperatures in the range of oxygen-to-carbon ratios of 0.40–2.50 regardless of the steam-to-carbon ratio employed. The maximum ammonia content (i.e., 40%) occurs at an oxygen-to-carbon ratio of 0.40, a steam-to-carbon ratio of 1.00 and a temperature of 100 °C. Hydrogen cyanide is favored at high temperatures and low oxygen-to-carbon ratios with a maximum of 3.18% occurring at an oxygen-to-carbon ratio of 0.40 and a steam-to-carbon ratio of 0.00 in the temperature range of 400 °C–500 °C. Increasing the system pressure shifts the equilibrium toward ammonia and hydrogen cyanide.  相似文献   

5.
《Journal of power sources》2006,157(1):422-429
Reduced-temperature solid oxide fuel cells (SOFCs) – with thin Ce0.85Sm0.15O1.925 (SDC) electrolytes, thick Ni–SDC anode supports, and composite cathodes containing La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) and SDC – were fabricated and tested with iso-octane/air fuel mixtures. An additional supported catalyst layer, placed between the fuel stream and the anode, was needed to obtain a stable output power density (e.g. 0.6 W cm−2 at 590 °C) without anode coking. The Ru-CeO2 catalyst produced CO2 and H2 at temperatures <350 °C, while H2 and CO became predominant above 500 °C. Power densities were substantially less than for the same cells with H2 fuel (e.g. 1.0 W cm−2 at 600 °C), due to the dilute (≈20%) hydrogen in the fuel mixture produced by iso-octane partial oxidation. Electrochemical impedance analysis showed a main arc that represented ≈60% of the total resistance, and that increased substantially upon switching from hydrogen to iso-octane/air.  相似文献   

6.
《Journal of power sources》2006,158(1):485-496
This paper describes a study of steam reforming of methane using unsupported nickel powder catalysts. The reaction yields were measured and the unsupported nickel powder surface was studied to explore its potential as a catalyst in internal or external reforming solid oxide fuel cells. The unsupported nickel catalyst used and presented in this paper is a pure micrometric nickel powder with an open filamentary structure, irregular ‘fractal-like’ surface and high external/internal surface ratio. CH4 conversion increases and coke deposition decreases significantly with the decrease of CH4:H2O ratio. At a CH4:H2O ratio of 1:2 thermodynamic equilibrium is achieved, even with methane residence times of only ∼0.5 s. The CH4 conversion is 98 ± 2% at 700 °C and no coke is generated during steam reforming which compares favorably with supported Ni catalyst systems. This ratio was used in further investigations to measure the hydrogen production, the CH4 conversion, the H2 yield and the selectivity of the CO, and CO2 formation. Methane-rich fuel ratios cause significant deviations of the experimental results from the theoretical model, which has been partially correlated to the adsorption of carbon on the surface according to TEM, XPS and elemental analysis. At the fuel: water ratio of 1:2, the unsupported Ni catalyst exhibited high catalytic activity and stability during the steam reforming of methane at low-medium temperature range.  相似文献   

7.
《Journal of power sources》2006,159(1):107-110
Hydrogen sorption kinetics of ball milled MgH2 with and without chemical additives were studied. We observed kinetics and capacity improvement with increasing the number of sorption cycles that contributed to the micro/nano cracking of MgH2 particles, shown by XRD and SEM studies. In addition, to investigate the proposed specific role of O2−-based additives on the sorption kinetics of MgH2, we have undertaken a comparative study evaluating the performances of MgH2 containing the NbCl5, CaF2 or Nb2O5 additives. At 300 °C, addition of NbCl5 and CaF2 improved the sorption capacity to 5.2 and 5.6 wt% within 50 min, respectively, in comparison to the required 80 min in the case of Nb2O5. This suggests the importance of the chemical nature of the catalyst for hydrogen sorption in MgH2. In addition, the catalyst specific surface area was shown to be very critical. High surface area Nb2O5 (200 m2 g−1), prepared by novel precipitation method, exhibits an excellent catalytic activity and helped to desorb 4.5 wt% of hydrogen from MgH2 within 80 min at a temperature as low as 200 °C.  相似文献   

8.
《Journal of power sources》2006,156(2):520-524
Because of the need for an efficient and inexpensive reforming catalyst, the objective of this work is to determine the feasibility of employing Mo2C catalyst for the steam reforming and oxy-steam reforming of the higher hydrocarbons typical of transportation fuels such as gasoline. It is shown that bulk Mo2C catalysts can successfully reform 2,2,4-trimethyl pentane (isooctane) to generate H2, CO and CO2 at very low steam/carbon ratios, without coke formation, eliminating the need for pre-reforming. Maximum hydrogen generation was observed at a S/C ratio of 1.3 and 1000 °C during SR reactions and S/C of 0.71, O2/C of 0.12 at 900 °C during oxidative steam reforming reactions.  相似文献   

9.
Effect of alkalis (NaOH, KOH and K2CO3) on liquefaction of EPFB (empty palm fruit bunch) biomass liquefaction was investigated under subcritical water conditions in a batch reactor operating at 270 °C and 20 bars for a period of 20 min. Catalytic performance and suitable biomass to water ratio that supported higher EPFB conversion, liquid hydrocarbons yield and lignin degradations were screened. Analytical results indicate that maximum of 68 wt% liquids were produced along with 72.4 wt% EPFB mass conversions and 65.6 wt% lignin degradation under 1.0 M K2CO3/2:10 (biomass/water) conditions. In comparison, the experiments that were performed in the absence of alkalis yielded only 30.4 wt% liquids, converted 36 wt% EPFB and degraded 24.3 wt% lignin. Furthermore, biomass to water ratios >2:10 decreased both solid mass conversion and liquid hydrocarbons' yield. The reactivity of the alkalis was in the order of K2CO3 > KOH > NaOH. The liquid compositions were dominantly phenols and esters; the highest value of phenol (60.1 wt% of liquid yield) was achieved in the case of K2CO3 (1.0 M) with 5 g EPFB/25 ml water ratio while 1.0 M NaOH yielded maximum esters (86.4 wt% of liquid yield). The alkali promoted process assisted with hot water treatments seemed promising for production of bio-oils from EPFB.  相似文献   

10.
In this study, carbon conversion was calculated from the data obtained with a real-time gas analyzer. In a lab-scale furnace, each biomass sample was pyrolyzed in a nitrogen environment and became biomass char. For preparation of the char, the furnace was electrically heated over 40 min up to the wall temperature of 850 °C, and maintained at the same temperature over 17 min. The furnace was again heated over 3 min to a temperature higher than 850 °C and then CO2 was injected. The biomass char was then gasified with CO2 under isothermal conditions. The reactivity of biomass char was investigated at various temperatures and CO2 concentrations. The VRM (volume reaction model), SCM (shrinking core model), and RPM (random pore model) were used to interpret the experimental data. For each model, the activation energy (E) and pre-exponential factor (A) of the biomass char-CO2 reaction were determined from gas-analysis data by using the Arrhenius equation. For the RPM, the apparent reaction order was determined. According to this study, it was found that the experimental data agreed better with the RPM than with the other two models. Through BET analyses, it was found that the structural parameter (ψ) of the surface area for the RPM was obtained as 4.22.  相似文献   

11.
The study focuses on hydrogen production from steam reforming of glycerol over nickel based catalyst promoted by zirconia and supported over ceria. Catalyst was prepared by the wet-impregnation method and characterized by BET surface area analysis, X-ray diffraction technique and scanning electron microscopy (SEM) analysis. The performance of the catalyst was evaluated in terms of hydrogen yield, selectivity and glycerol conversion at 700 °C in a tubular fixed bed reactor. The effect of glycerol concentration in feed, space time (W/FAO), temperature and time on stream (TOS) was analyzed for the catalyst Ni–ZrO2/CeO2 which showed the complete conversion of glycerol and high H2 yield that corresponds to 3.95 mol of H2 out of 7 mol. Thermodynamic analysis was also carried out using Aspen HYSYS for system having glycerol concentration 10 wt% and 20 wt% and experimental results were compared with thermodynamics. Kinetic study was carried out for the steam reforming of glycerol over Ni–ZrO2/CeO2 catalyst using the power law model. The values of activation energy and order of reaction were found to be 43.4 kJ/mol and 0.3 respectively.  相似文献   

12.
《Journal of power sources》2002,111(2):283-287
Hydrogen production for fuel cells through methane (CH4) reforming at low temperatures has been investigated both thermodynamically and experimentally. From the thermodynamic equilibrium analysis, it is concluded that steam reforming of CH4 (SRM) at low pressure and a high steam-to-CH4 ratio can be achieved without significant loss of hydrogen yield at a low temperature such as 550 °C. A scheme for the production of hydrogen for fuel cells at low temperatures by burning the unconverted CH4 to supply the heat for SRM is proposed and the calculated value of the heat-balanced temperature is 548 °C. SRM with and/or without the presence of oxygen at low temperatures is experimentally investigated over a Ni/Ce–ZrO2/θ-Al2O3 catalyst. The catalyst shows high activity and stability towards SRM at temperatures from 400 to 650 °C. The effects of O2:CH4 and H2O:CH4 ratios on the conversion of CH4, the hydrogen yield, the selectivity for carbon monoxide, and the H2:CO ratio are investigated at 650 °C with a constant CH4 space velocity. Results indicate that CH4 conversion increases significantly with increasing O2:CH4 or H2O:CH4 ratio, and the hydrogen content in dry tail gas increases with the H2O:CH4 ratio.  相似文献   

13.
Applicability of gulfweed as feedstock for a biomass-to-liquid (BTL) process was studied for both production of gas with high syngas (CO + H2) content via gasification of gulfweed and removal of gaseous impurities using char obtained in the gasification. Gulfweed as aqueous biomass was gasified with He/CO2/O2 using a downdraft fixed-bed gasifier at ambient pressure and 900 °C at equivalence ratios (ER) of 0.1–0.3. The syngas content increased while the conversion to gas on a carbon basis decreased with decreasing ER. At an ER of 0.1 and He/CO2/O2 = 0/85/15%, the syngas content was maximized at 67.6% and conversion to gas on a carbon basis was 94.2%. The behavior of the desulfurization using char obtained during the gasification process at ER = 0.1 and He/CO2/O2 = 0/85/15% was investigated using a downdraft fixed-bed reactor at 250–550 °C under 3 atmospheres (H2S/N2, COS/N2, and a mixture of gases composed of CO, CO2, H2, N2, CH4, H2S, COS, and steam). The char had a higher COS removal capacity at 350 °C than commercial activated carbon because (Ca,Mg)S crystals were formed during desulfurization. The char simultaneously removed H2S and COS from the mixture of gases at 450 °C more efficiently than did activated carbon. These results support this novel BTL process consisting of gasification of gulfweed with CO2/O2 and dry gas cleaning using self-supplied bed material.  相似文献   

14.
Al2O3–ZrO2 (AZ) xerogel supports prepared by a sol-gel method were calcined at various temperatures. Ni/Al2O3–ZrO2 (Ni/AZ) catalysts were then prepared by an impregnation method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of calcination temperature of AZ supports on the catalytic performance of Ni/AZ catalysts in the steam reforming of LNG was investigated. Crystalline phase of AZ supports was transformed in the sequence of amorphous γ-Al2O3 and amorphous ZrO2  θ-Al2O3 and tetragonal ZrO2   + α)-Al2O3 and (tetragonal + monoclinic) ZrO2  α-Al2O3 and (tetragonal + monoclinic) ZrO2 with increasing calcination temperature from 700 to 1300 °C. Nickel oxide species were strongly bound to γ-Al2O3 and θ-Al2O3 in the Ni/AZ catalysts through the formation of solid solution. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AZ supports. Nickel surface area of Ni/AZ catalysts was well correlated with catalytic performance of the catalysts. Among the catalysts tested, Ni/AZ1000 (nickel catalyst supported on AZ support that had been calcined at 1000 °C) with the highest nickel surface area showed the best catalytic performance. Well-developed and pure tetragonal phase of ZrO2 in the AZ1000 support played an important role in the adsorption of steam and the subsequent spillover of steam from the support to the active nickel.  相似文献   

15.
《Journal of power sources》2006,155(2):353-357
Two types of solid oxide fuel cells (SOFCs), with thin Ce0.85Sm0.15O1.925 (SDC) or 8 mol% Y2O3-stabilized ZrO2 (YSZ) electrolytes, were fabricated and tested with iso-octane/air fuel mixtures. An additional Ru–CeO2 catalyst layer, placed between the fuel stream and the anode, was needed to obtain a stable output power density without anode coking. Thermodynamic analysis and catalysis experiments showed that H2 and CO were primary reaction products at ≈750 °C, but that these decreased and H2O and CO2 increased as the operating temperature dropped below ≈600 °C. Power densities for YSZ cells were 0.7 W cm−2 at 0.7 V and 790 °C, and for SDC cells were 0.6 W cm−2 at 0.6 V and 590 °C. Limiting current behavior was observed due to the relatively low (≈20%) H2 content in the reformed fuel.  相似文献   

16.
《能源学会志》2020,93(6):2344-2354
Residues of leek, cabbage and cauliflower from the market places as representatives of lignocellulosic biomass were processed via hydrothermal gasification to produce energy fuel. The experiments were carried out in a batch reactor at temperatures 300, 400, 500 and 600 °C and corresponding pressures varying in the range of 7.5–43 MPa. Natural mineral additives trona, dolomite and borax were used as homogenous catalysts to determine their effects on the gasification. More than 70 wt% of carbon in vegetable residue samples were detected in the gas phase after the hydrothermal gasification process at 600 °C. The addition of trona mineral further promoted the gasification reactions and as a result, less than 5 wt% carbon remained in the solid residue at the same temperature, degrading the biomass samples into gas and liquid products. The fuel gas with the highest calorific value was recorded to be 25.6 MJ/Nm3, from the hydrothermal gasification of cabbage at 600 °C, when dolomite was used as the homogeneous catalyst. The liquid products obtained in the aqueous phase were detected as organic acids, aldehydes, ketones, furfurals and phenols. The gas products were consisted of hydrogen, carbon dioxide, methane, and as minors; carbon monoxide and low molecular weight hydrocarbons (ethane, propane, etc.). Above 500 °C, all biomass samples yielded 50–55 vol% of CH4 and H2 while the CO2 composition was around 40 vol% as the gas product.  相似文献   

17.
The purpose of this study was to investigate the production of NaBH4 as hydrogen storage material and testing its hydrogen storage capacity in presence of catalyst. Synthesis of NaBH4 was investigated with NaH and trimethyl borate which was also produced in previous studies. Different reaction temperatures, times and reactant ratios constitute the three parameters of the production process. The best combination determined by FT-IR, XRF and XRD analyses, was found to be 1.413 (mol/mol) TMB over NaH at 250 °C for 90 min. In order to increase the NaBH4 purity ethylene diamine was used as solvent at 75 °C. After 4 extraction and crystallization processes 85.17% NaBH4 purity was obtained. Moreover, hydrogen content of the product NaBH4 was measured in a system with different catalysts since catalyst efficiency is important in decreasing the water dependence of dehydrogenation. CoCl2 catalyst proved best by taking out more hydrogen, both from the NaBH4 structure and from water.  相似文献   

18.
Improved interfacial resistance was observed in lithium cells by the use of new additives. The additives, nitrile sucrose and nitrile cellulose and their lithium salts, were evaluated in polyvinylidene difluoride (PVDF) thin-film gelled electrolytes containing a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). The electrochemical properties of the films with and without the additives were measured as a function of temperature and compared. The interfacial resistance (Rin) of the films with the additives was significantly lower than that without the additives, especially at sub-ambient temperatures. For example, the Rin at −20°C for the films with additives was around 7000 Ω cm2 and that for the films without the additives was >20,000 Ω cm2. Results obtained from using the additives in lithium-ion (Li-ion) cells show significant improvements in the low frequency resistance of the cells.  相似文献   

19.
《Journal of power sources》2006,158(1):103-109
Proton-conducting composite material was synthesized from 1-butyl-3-methyl-imidazolium chloride (BMImCl) and 12-phosphotungstic acid (PWA). The structure, assistant catalytic effect and ionic conductivity of the composites for the as-synthesized, 200 and 400 °C annealed samples were studied, respectively. The as-synthesized salt was crystal and kept Keggin structure even being annealed at 400 °C, but the organic part was partly decomposed with increasing of the annealing temperature. The partly decomposed BMIm/PWA salt formed by annealing at 400 °C associated with Pt catalyst had excellent assistant catalytic effect on methanol electro-oxidation and displayed a high proton conductivity of 2 mS cm−1 at 30 °C under 96% relative humidity condition.  相似文献   

20.
《Journal of power sources》2004,128(2):135-144
The preparation and subsequent oxidation of nickel cathodes modified by impregnation with zinc oxide (ZnO) were evaluated by surface and bulk analysis. The electrochemical behaviors of ZnO impregnated NiO cathodes was also evaluated in a molten 62 mol% Li2CO3 + 38 mol% K2CO3 eutectic at 650 °C by electrochemical impedance spectroscopy (EIS) as a function of ZnO content and immersion time. The ZnO impregnated nickel cathodes showed the similar porosity, pore size distribution and morphology to the reference nickel cathode. The stability tests of ZnO impregnated NiO cathodes showed that the ZnO additive could dramatically reduce the solubility of NiO in a eutectic carbonate mixture under the standard cathode gas condition. The impedance spectra for cathode materials show important variations during the 100 h of immersion. The incorporation of lithium in its structure and the low dissolution of nickel oxide and zinc oxide are responsible of these changes. After that, the structure reaches a stable state. The cathode material having 2 mol% of ZnO showed a very low dissolution and a good catalytic efficiency close to the NiO value. We thought that 2 mol% ZnO/NiO materials would be able to adapt as alternative cathode materials for MCFCs.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号