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1.
The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO2 sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.  相似文献   

2.
A pathway for hydrogen production from supercritical water reforming of glycerol integrated with in situ CO2 removal was proposed and analyzed. The thermodynamic analysis carried out by the minimizing Gibbs free energy method of three glycerol reforming processes for hydrogen production was investigated in terms of equilibrium compositions and energy consumption using AspenPlus™ simulator. The effect of operating condition, i.e., temperature, pressure, steam to glycerol (S/G) ratio, calcium oxide to glycerol (CaO/G) ratio, air to glycerol (A/G) ratio, and nickel oxide to glycerol (NiO/G) ratio on the hydrogen production was investigated. The optimum operating conditions under maximum H2 production were predicted at 450 °C (only steam reforming), 400 °C (for autothermal reforming and chemical looping reforming), 240 atm, S/G ratio of 40, CaO/G ratio of 2.5, A/G ratio of 1 (for autothermal reforming), and NiO/G ratio of 1 (for chemical looping reforming). Compared to three reforming processes, the steam reforming obtained the highest hydrogen purity and yield. Moreover, it was found that only autothermal reforming and chemical looping reforming were possible to operate under the thermal self-sufficient condition, which the hydrogen purity of chemical looping reforming (92.14%) was higher than that of autothermal reforming (52.98%). Under both the maximum H2 production and thermal self-sufficient conditions, the amount of CO was found below 50 ppm for all reforming processes.  相似文献   

3.
Chemical looping steam reforming (CLSR) of ethanol using oxygen carriers (OCs) for hydrogen production has been considered a highly efficient technology. In this study, NiO/MgAl2O4 oxygen carriers (OCs) were employed for hydrogen production via CLSR with and without CaO sorbent for in-situ CO2 removal (sorption enhanced chemical looping steam reforming, SE-CLSR). To find optimal reaction conditions of the CLSR process, including reforming temperatures, the catalyst mass, and the NiO loadings on hydrogen production performances were studied. The results reveal that the optimal temperature of OCs for hydrogen production is 650 °C. In addition, 96% hydrogen selectivity and a 'dead time' (the reduced time of OCs) less than 1 minute is obtained with the 1 g 20NiO/MgAl2O4 catalysts. The superior catalytic activity of 20NiO/MgAl2O4 is due to the maximal quantity of NiO loadings providing the most Ni active surface centers. High purity hydrogen is successfully produced via CLSR coupling with CaO sorbent in-situ CO2 removal (SE-CLSR), and the breakthrough time of CaO is about 20 minutes under the condition that space velocity was 1.908 h?1. Stability CLSR experiments found that the hydrogen production and hydrogen selectivity decreased obviously from 207 mmol to 174 mmol and 95%–85% due to the inevitable OCs sintering and carbon deposition. Finally, stable hydrogen production with the purity of 89%~87% and selectivity of 96%~93% was obtained in the modified stability SE-CLSR experiments.  相似文献   

4.
This study investigates hydrogen production by thermo-catalytic steam methane reforming over lanthanum strontium cobalt ferrite supported Nickel (Ni/LSCF) and commercial Ni/αAl2O3 catalysts. The Ni/LSCF catalyst was synthesized using wet impregnation method and characterized by XRD, TEM, SEM, EDX, N2-physisorption analysis, and H2-TPR. The characterization analyses show that Ni/LSCF and Ni/αAl2O3 possess the required physicochemical properties to catalyze the steam methane reforming reaction. The activity of the Ni/LSCF catalyst in steam methane reforming at 750 °C, 800 °C, and 850 °C resulted in CH4 conversions of 73.46%, 78.67%, and 87.56%, respectively. In addition, hydrogen (H2) yields of 64.34%, 72.57%, and 82.56% were obtained from the steam methane reforming at 750 °C, 800 °C, and 850 °C, respectively over the Ni/LSCF catalyst. The Ni/LSCF catalyst was found to have higher activities in term of CH4 conversion and H2 yield compare to the commercial Ni/αAl2O3. However, the stability test conducted at 480 min time on stream (TOS) revealed that the commercial Ni-αAl2O3 was more stable in the steam methane reforming than the Ni/LSCF catalyst. The characterization of the used catalysts by TEM, XRD and TGA shows evidence of carbon deposition mostly on the used Ni/LSCF catalyst.  相似文献   

5.
Transition metal catalysts widely used in refineries are provided as oxides and require pre-reduction to become activated. The auto-reduction of a NiO/Al2O3 catalyst with acetic acid (HAc) followed by HAc steam reforming was investigated in a packed bed reactor. Effects of temperature and molar steam to carbon ratio (S/C) on reduction kinetics and catalyst performance were analysed. Results showed that a steady steam reforming regime along with complete NiO reduction could be obtained after a coexistence stage of reduction and reforming. A 2D nucleation and nuclei growth model fitted the NiO auto-reduction. The maximum reduction rate constant was attained at S/C = 2. Steam reforming activity of the auto-reduced catalyst was just below that of the H2-reduced catalyst, probably attributed to denser carbon filament formation and larger loss of active Ni. Despite this, a H2 yield of 76.4% of the equilibrium value and HAc conversion of 88.97% were achieved at 750 °C and S/C = 3.  相似文献   

6.
Production of high purity hydrogen (<50 ppm CO) by steam–iron process (SIP) from a synthetic sweetened biogas has been investigated making use of a natural iron ore containing up to 81 wt% of hematite (Fe2O3) as oxygen carrier. The presence of a lab-made catalyst (NiAl2O4 with NiO excess above its stoichiometric composition) was required to carry out the significant transformation of mixtures of methane and carbon dioxide in hydrogen and carbon monoxide by methane dry reforming reaction. Three consecutive sub-stages have been identified along the reduction stage that comprise A) the combustion of CH4 by lattice oxygen of NiO and Fe2O3, B) catalyzed methane dry reforming and C) G–G equilibrium described by the Water-Gas-Shift reaction. Oxidation stages were carried out with steam completing the cycle. Oxidation temperature was always kept constant at 500 °C regardless of the temperature used in the previous reduction to minimize the gasification of eventual carbon deposits formed along the previous reduction stage. The presence of other oxides different from hematite in minor proportions (SiO2, Al2O3, CaO and MgO to name the most significant) confers it an increased thermal resistance against sintering respecting pure hematite at the expense of slowing down the reduction and oxidation rates. A “tailor made” hematite with additives (Al2O3 and CeO2) in minor proportions (2 wt%) has been used to stablish comparisons in performance between natural and synthetic iron oxides. It has been investigated the effect of the reduction temperature, the proportion of methane to carbon dioxide in the feed (CH4:CO2 ratio) and the number of repetitive redox cycles.  相似文献   

7.
Catalytic steam reforming for producing high quality syngas from biomass fuel gas was studied over monolithic NiO/porous ceramic catalysts in a fixed-bed reactor. Effects of reaction temperature, steam to carbon (S/C) ratio, and nickel loading content on catalyst performance were investigated. Results indicated that the NiO/porous ceramic monolith catalyst had a good ability to improve bio-fuel gas quality. H2 yield, H2 + CO content, and H2/CO ratio in produced gas were increased when reaction temperature was increased from 550 to 700 °C. H2 yield was increased from 28.1% to 40.2% with S/C ratio increased from 1 to 2. And the yield of hydrogen was stabilized with the further increase of S/C ratio. Catalyst activity was not always enhanced with increased nickel content, when NiO loading content reaches 5.96%, serious aggregation and sintering of active composition on catalyst surface occur. The best performance, in terms of H2 yield, is obtained with 2.50% NiO content at reaction temperature of 700 °C and S/C ratio of 2.  相似文献   

8.
Autothermal reforming of ethanol on zirconia-supported Rh and Pt mono- and bimetallic catalysts (0.5 wt-% total metal loading) was studied as a source of H2-rich gas for fuel cells. The results were compared with those obtained on a commercial steam reforming catalyst (15 wt-% NiO/Al2O3). The Rh-containing catalysts exhibited the highest selectivity for H2 production and were stable in 24 h experiments. The formation of carbonaceous deposits was lower on the noble metal catalysts than on the commercial NiO/Al2O3 catalyst. Thus, the Rh-containing catalysts are more suitable than the commercial NiO/Al2O3 catalysts for the ATR of ethanol.  相似文献   

9.
Ni catalysts were prepared by wet impregnation of three different supports: alumina, niobia and 10 wt.% niobia/alumina, prepared by (co)precipitation. The catalysts were evaluated on steam reforming of glycerol at 500 °C, for 30 h. The catalyst supported on Nb2O5/Al2O3 presented the best performance, with higher conversion into gas (80%) during all reaction time and hydrogen yield of 50%. Alumina supported catalyst showed higher deactivation and lower hydrogen yield. All catalysts showed coke formation, but it was formed in larger amount on the catalysts supported on single oxides. A depth study was conducted to evaluate the effect of reaction variables as space velocity, glycerol concentration in feed and temperature on the catalytic performance of the Nb2O5/Al2O3 catalyst. Kinetic study was also performed for this catalyst using two different approaches, obtaining glycerol and steam orders, as well as the apparent activation energy.  相似文献   

10.
An iron-calcium hybrid catalyst/absorbent (Ca–Al–Fe) is developed by a two-step sol-gel method to enhance tar conversion, cyclic CO2 capture and mechanical strength of absorbent for hydrogen production in calcium looping gasification. The developed catalyst/absorbent consists of CaO and brownmillerite (Ca2Fe2O5) with mayenite (Ca12Al14O33) as inert support. Comparing with three candidate absorbents without Ca2Fe2O5 or Ca12Al14O33, cyclic carbonation reactivity and mechanical strength of Ca–Al–Fe are largely promoted. Meanwhile, Ca–Al–Fe approaches the maximum conversion rate of 1-methyl naphthalene (1-MN) with enhanced hydrogen yield around 0.15 mol/(h·g) under reforming conditions of present study. Ca–Al–Fe also shows the largest CO2 absorption and lowest coke deposition. Influences of operation variables on 1-MN reforming are evaluated and recommended conditions can be iron to CaO mass ratio of 10%, reaction temperature of 800 °C and steam to carbon in 1-MN mole ratio of 2.0. Ca–Al–Fe hybrid catalyst/absorbent presents good potential to be applied in future.  相似文献   

11.
Supported Ni catalysts have been investigated for hydrogen production from steam reforming of glycerol. Ni loaded on Al2O3, La2O3, ZrO2, SiO2 and MgO were prepared by the wet-impregnation method. The catalysts were characterized by nitrogen adsorption–desorption, X-ray diffraction and scanning electron microscopy. The characterization results revealed that large surface area, high dispersion of active phase on support, and small crystalline sizes are attributes of active catalyst in steam reforming of glycerol to hydrogen. Also, higher basicity of catalyst can limit the carbon deposition and enhance the catalyst stability. Consequently, Ni/Al2O3 exhibited the highest H2 selectivity (71.8%) due to small Al2O3 crystallites and large surface area. Response Surface Methodology (RSM) could accurately predict the experimental results with R-square = 0.868 with only 4.5% error. The highest H2 selectivity of 86.0% was achieved at optimum conditions: temperature = 692 °C, feed flow rate = 1 ml/min, and water glycerol molar ratio (WGMR) 9.5:1. Also, the optimization results revealed WGMR imparted the greatest effect on H2 selectivity among the reaction parameters.  相似文献   

12.
An original kinetic model has been proposed for the reforming of the volatiles derived from biomass fast pyrolysis over a commercial Ni/Al2O3 catalyst. The pyrolysis-reforming strategy consists of two in-line steps. The pyrolysis step is performed in a conical spouted bed reactor (CSBR) at 500 °C, and the catalytic steam reforming of the volatiles has been carried out in-line in a fluidized bed reactor. The reforming conditions are as follows: 600, 650 and 700 °C; catalyst mass, 0, 1.6, 3.1, 6.3, 9.4 and 12.5 g; steam/biomass ratio, 4, and; time on stream, up to 120 min. The integration of the kinetic equations has been carried out using a code developed in Matlab. The reaction scheme takes into account the individual steps of steam reforming of bio-oil oxygenated compounds, CH4 and C2-C4 hydrocarbons, and the WGS reaction. Moreover, a kinetic equation for deactivation has been derived, in which the bio-oil oxygenated compounds have been considered as the main coke precursors. The kinetic model allows quantifying the effect reforming conditions (temperature, catalyst mass and time on stream) have on product distribution.  相似文献   

13.
Mo-promoted alumina supported Ni catalysts were prepared through a conventional impregnation method and tested in dry reforming of methane (DRM) at temperatures from 550 to 850 °C. The catalysts were characterized by means of H2-temperature programmed reduction (H2-TPR), CO2-temperature programmed desorption (CO2-TPD), X-ray diffraction (XRD), N2 physisorption and Raman spectroscopy. Mo-promotion caused a reduction in the DRM catalytic activity. The weaker interaction between NiO species and the alumina support, the formation of a MoNi4 phase, and the lower basicity of this Ni-Mo/Al2O3 catalyst were identified as the main causes for its lower activity. However, pre-reducing the Ni-Mo/Al2O3 catalyst at temperatures lower than 700 °C, instead of 900 °C, resulted in a considerable increase of its catalytic activity. This was mainly due to the formation of a separate Ni0 phase that did not interact with Mo and to an increase in medium strength basicity.  相似文献   

14.
Hydrogen production from rice husk was carried out via a two-stage system combining CLG (calcium looping gasification) using Ca(OH)2 adsorbent in a bubbling fluidized bed and catalytic reforming with Ce–Ni/γAl2O3 catalyst in a connected fixed bed. The results show that the maximum H2 concentration (69.16 vol%) and H2 yield (11.86 mmol g−1rice husk) are achieved at Ca/C (Ca(OH)2 to carbon molar ratio) = 1.5, H2O/C (H2O to carbon molar ratio) = 1.5, Tg (gasification temperature) = 500 °C, Tc (catalytic temperature) = 800 °C. The supplementation of fresh Ca(OH)2 at Ca/C of 0.5 during calcination helps to activate the regenerated CaO by hydration, maintaining its carbonation activity and CO2 adsorption. Ce–Ni/γAl2O3 catalyst promotes water gas shift (WGS), steam methane reforming (SMR), and C2–C3 hydrocarbons reforming, also exhibits excellent activity stability to maintain H2 concentration and H2 yield above 67.21 vol% and 11.67 mmol g−1rice husk, respectively, during 5 lifetime tests.  相似文献   

15.
Chemical looping gasification (CLG) involves the use of an oxygen carrier (OC) which transfers oxygen from air to solid fuel to convert the fuel into synthesis gas, and the traditional gasifying agents such as oxygen-enriched air or high temperature steam are avoided. In order to improve the reactivity of OC with biomass char, facilitating biomass high-efficiency conversion, a compound Fe/Ni bimetallic oxide (NiFe2O4) was used as an OC in the present work. Effect of OC content and oxygen sources on char gasification were firstly investigated through a TG reactor. When the OC content in mixture sample attains 65 wt.%, the sample shows the maximum weight loss rate at relatively low temperature, indicating that it is very favorable for the redox reactions between OC and biomass char. The NiFe2O4 OC exhibits a good performance for char gasification, which is obvious higher than that of individual Fe2O3 OC and mechanically mixed Fe2O3 + NiO OC due to the Fe/Ni synergistic effect in unique spinel structure. According to the TGA experimental results, effect of the steam content and cyclic numbers on char gasification were investigated in a fixed bed reactor. Either too low steam content or too high steam content doesn't facilitate the char gasification. And suitable steam content of 56.33% is determined with maximum carbon conversion of 88.12% and synthesis gas yield of 2.58 L/g char. The reactivity of NiFe2O4 OC particles shows a downtrend within 20 cycles (~64 h) due to the formation of Fe2O3 phase, which is derived from the iron element divorced from the Fe/Ni spinel structure. Secondly, the sintering of OC particles and ash deposit on the surface are also the reasons for the deactivation of NiFe2O4 OC. However, the carbon conversion and synthesis gas yield at the 20th cycle are still higher than those of the blank experiment. It indicates that the reactivity of NiFe2O4 OC can be maintained at a relatively long time and NiFe2O4 material can be used as a good OC candidate for char gasification in the long time running.  相似文献   

16.
CaO doped Ni/MCF catalysts were prepared by conventional incipient wetness impregnation and sol-gel methods for the study of methane dry reforming reaction. The fresh and used catalysts were characterized using H2 temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), thermogravimetry (TG), differential scanning calorimetry (DSC) and O2 temperature-programmed oxidation (O2-TPO). XRD exhibited that CaO and Ni particles are dispersed on the surface of catalyst. The Ni:CaO ratio was adjusted for the improvement of pore textural properties on behalf of enhancement of metal particle dispersion for increased catalytic performance and anti-coking. The catalytic performance and stability of the catalysts for methane dry reforming reaction were studied at 700–750 °C at atmospheric pressure with GHSV of 24000 mL g?1h?1 having same feed ratio of CH4:CO2 = 1. Experimental results exhibited that catalyst prepared by a sol-gel method showed superior catalytic activity, stability and resisted carbon deposition than catalyst prepared incipient wetness impregnation method. Among all tested catalysts 9CaO 9Ni/MCF catalyst remained the best for catalytic performance and anti-coking activity due to higher metal dispersion with small metal particles, as well as the synergetic effect between CaO and Ni. During 75 h stability test over the catalyst 9CaO 9Ni/MCF the CH4 and CO2 conversion remained 91% and 99% respectively.  相似文献   

17.
Propane steam reforming (PSR) for the production of H2 was catalyzed by a NiO/K-AlSixOy catalyst synthesized with various Si/Al ratios (Si/Al = 0, 0.3, 0.5, 0.7, and 1.0). The effect of the Si/Al ratio on the acidity of the NiO/K-AlSixOy catalyst for PSR was investigated. NiO/K-AlSixOy gave a higher H2 selectivity and stability during PSR than NiO/K-SiO2 and NiO/K-Al2O3. The NH3-TPD results showed that the acid quantity and strength of NiO/K-AlSixOy changed significantly depending on the Si/Al ratio. With an increased Si/Al ratio, the densities of both weak and strong acid sites increased. The C3H8- and CO-TPD results indicated that desorption amounts increased significantly in all NiO/K-AlSixOy catalysts relative to those of NiO/K-SiO2 and NiO/K-Al2O3, and the adsorption amount increased with the Si/Al ratio. PSR results showed that the NiO/K-AlSixOy catalyst exhibited much better stability than the NiO/K-SiO2 and NiO/K-Al2O3 catalysts. This study confirms the following facts: when the acidity is appropriately adjusted for the catalyst, adsorption of the reaction gas increases, which eventually increases the reaction rate and also inhibits strong sintering between the nickel and the Al2O3 support. As a result, deterioration of the catalyst can be reduced.  相似文献   

18.
The process of thermocatalytic reforming of cellulose has been studied by using solar energy. It has been established that the process of conversion proceeds through depolymerization stages of cellulose with formation of hexoses including following the dehydration of three molecules water, first and secondary conversion. It is shown that carbohydrate of compound [6C(H2O)3 undergoes thermocatalytic conversion by water steam. In addition, the possibility of obtaining synthesis-gas [H2 + CO] with temperatures of 700–750 °C on the catalyst Pt/Al2O3 is shown. The dependence of gasiformation on temperature and degree of dilution by water steam has been studied.  相似文献   

19.
In this novel paper, a technique for hydrogen production route of CaO sorption‐enhanced methane steam reforming (SEMSR) thermally coupled with chemical looping combustion (CLC) was presented (CLC‐SEMSR), which perceived as an improvement of previous methane steam reforming (MSR) thermally coupled with CLC technology (CLC‐MSR). The application of CLC instead of furnace achieves the inherent separation of CO2 from flue gas without extra energy required. The required heat for the reformer is provided by thermally coupling CLC. The addition of CaO sorbents can capture CO2 as it is formed from the reformer gas to the solid phase, displacing the normal MSR equilibrium restrictions and obtaining higher purity of H2. The Aspen Plus was used to simulate this novel process on the basis of thermodynamics. The performances of this system examined included the composition of reformer gas, yield of reformer gas (YRg), methane conversion (αM), the overall energy efficiency (η), and exergy efficiency (φ) of this process. The effects of the molar ratio of CaO to methane for reforming (Ca/M) in the range of 0–1.2, the molar ratio of methane for combustion to methane for reforming (M(fuel)/M) in the range of 0.1–0.3, and the molar ratio of NiO to methane for reforming (Ni/M) in the range of 0.4–1.2 were investigated. It has been found to be favored by operating under the conditions of Ca/M = 1, M(fuel)/M = 0.2, and Ni/M = 0.8. The most excellent advantage of CLC‐SEMSR was that it could obtain higher purity of H2 (95%) at lower operating temperature (655 °C), as against H2 purity of 77.1% at higher temperature (900 °C) in previous CLC‐MSR. In addition, the energy efficiency of this process could reach 83.3% at the optimal conditions. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

20.
Cold spray was employed as a novel method to prepare NiO/Al2O3 primary steam reforming catalyst coating for hydrogen production. The coating microstructure was characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) before and after reforming reactions. The catalytic coating performance was examined through methane steam reforming (SRM) in a microreactor. Results showed that NiO/Al2O3 coating was successfully deposited on the stainless steel substrate by cold spray. The thickness of the coating was about 50 μm. It presented a rough surface and porous structure. Since temperature of the cold spray process is low, no phase changes occurred to NiO/Al2O3 during deposition. However the particle size in the coating became smaller compared with the feedstock due to its smashing. It was found that the cold-sprayed catalytic coating was active for SRM at high space velocity although filamentous carbon was formed on its surface. After reaction there was no obvious peeling off of the coating indicating a good bonding between the coating and substrate.  相似文献   

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