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1.
The reforming of hot gas generated from biomass gasification and high temperature gas filtration was studied in order to reach the goal of the CHRISGAS project: a 60% of synthesis gas (as x(H2)+ x(CO) on a N2 and dry basis) in the exit gas, which can be converted either into H2 or fuels. A Ni-MgAl2O4 commercial-like catalyst was tested downstream the gasification of clean wood made of saw dust, waste wood and miscanthus as herbaceous biomass. The effect of the temperature and contact time on the hydrocarbon conversion as well as the characterization of the used catalysts was studied. Low (<600 °C), medium (750°C–900 °C) and high temperature (900°C–1050 °C) tests were carried out in order to study, respectively, the tar cracking, the lowest operating reformer temperature for clean biomass, the methane conversion achievable as function of the temperature and the catalyst deactivation. The results demonstrate the possibility to produce an enriched syngas by the upgrading of the gasification stream of woody biomass with low sulphur content. However, for miscanthusthe development of catalysts with an enhanced resistance to sulphur poison will be the key point in the process development.  相似文献   

2.
Tars in biomass gasification systems need to be removed to avoid damaging and clogging downstream pipes or equipment. In this study, Ni-based catalysts were made by mechanically mixing NiO and char particles at various ratios. Catalytic performance of the Ni/char catalysts was studied and compared with performance of wood char and coal char without Ni for syngas cleanup in a laboratory-scale updraft biomass gasifier. Reforming parameters investigated were reaction temperature (650–850 °C), NiO loading (5–20% of the weight of char support), and gas residence time (0.1–1.2 s). The Ni/coalchar and Ni/woodchar catalysts removed more than 97% of tars in syngas at 800 °C reforming temperature, 15% NiO loading, and 0.3 s gas residence time. Analysis of syngas composition indicated that concentrations of H2 and CO in syngas significantly. Furthermore, performance of the Ni/coalchar catalyst was continuously tested for 8 h. There was slight deactivation of the catalyst in the early stage of tar/syngas reforming; however, the catalyst was able to stabilize soon after. It was concluded that chars especially coal char can be an effective and inexpensive support of NiO for biomass gasification tar removal and syngas conditioning.  相似文献   

3.
This study investigates the enhancement of tar and trace gaseous pollutants (e.g. hydrogen sulfide (H2S) and hydrogen chloride (HCl) removal efficiency derived from rice straw gasification using an integrated hot-gas cleaning system. A bubbling fluidized bed gasifier was used by controlling the temperature at 800 °C and equivalence ratio (ER) ranging 0.2 to 0.4. The hot gas cleaning system was operated at 250 °C and designed to combine three types of absorbents including zeolite, calcined dolomite, and activated carbon. Tar, H2S, and HCl removal efficiency and enhanced hydrogen production were also discussed. The experimental results indicated that light fraction tar removal efficiency was higher than 90% and the overall tar removal efficiency was approximately 70%. In the case of ER 0.4, the syngas tar content was decreased from 71.88 g/Nm3 (without hot gas cleaning system) to 16.53 g/Nm3 (with hot gas cleaning system). The tar removal efficiency is nearly 77% using the hot gas cleaning system. The HCl and H2S removal efficiency ranged from 94% to 98% and from 80.7% to 83.92%, respectively. In the case of ER 0.3 and with the hot gas cleaning system, the HCl and H2S concentrations in cleaned syngas gas were less than 40 ppm and 100 ppm, respectively. Meanwhile, the hydrogen concentration of produced gas was also increased from 6.82% to 9.83% with hot gas cleaning system used. It means that the hot gas cleaning system can effectively remove HCl and H2S from produced gas in gasification, but also it has good potential for improving syngas quality and enhancing gas turbine application in the future.  相似文献   

4.
Methane reforming is the most important and economical process for hydrogen and syngas generation. In this work, the dynamic simulation of methane steam reforming in an industrial membrane reformer for synthesis gas production is developed. A novel deactivation model for commercial Ni-based catalysts is proposed and the monthly collected data from an existing reformer in a domestic methanol plant is used to optimize the model parameters. The plant data is also employed to check the model accuracy. It was observed that the membrane reformer could compensate for the catalyst deactivating effect.In order to assure the long membrane lifetime and decrease the unit price, the membrane reformer with 5 μm thick Pd on stainless steel supports is modeled at the temperature below the maximum operating temperature of Pd based membranes (around 600 °C). The dynamic modeling showed that the methane conversion of 76% could be achieved at a moderate temperature of 600 °C for an industrial membrane reformer. The cost-effective generation of syngas with an appropriate H2/CO ratio of 2.6 could be obtained by membrane reformer. This is while the conventional reformer exhibits a maximum conversation of 64 at 1200 °C challenging due to its high syngas ratio (3.7). On the other hand, the pure hydrogen from membrane reformer can supply part of the ammonia reactor feed in an adjacent ammonia plant.  相似文献   

5.
In this study, innovative Ni-based catalysts supported by five typical slag carriers (magnesium slag (MS), steel slag (SS), blast furnace slag (BFS), pyrite cinder (PyC) and calcium silicate slag (CSS)) were prepared by wet impregnation. With the prepared catalysts and Ni/γ-Al2O3 catalyst, catalytic reforming of pyrolysis volatiles from pine sawdust for syngas production and tar removal was investigated. The catalysts were characterized by BET, XRD, SEM, TEM and Raman. The catalytic performances of the six catalysts were decreasing in the following order: Ni/MS > Ni/γ-Al2O3 > Ni/SS > Ni/BFS > Ni/CSS > Ni/PyC. Ni/MS catalyst exhibited excellent catalytic reactivity as well as thermal stability in terms of tar conversion (95.19%), gas yield (1.46 Nm3/kg) and CO2 capture ability (CO2 yield of 0.5%). Both amorphous carbon and graphite-type carbon were formed on the catalysts after catalytic reforming and the D/G ratio (the relative intensity ratio of the D-band to the G-band) was positively correlated to the catalytic activity.  相似文献   

6.
High-performance and inexpensive catalysts play a large role in effective removal of biomass tar produced during biomass gasification. In this study, raw wood, with long, through, but distorted channels and a low tortuosity, was selected as a support. A layered NiCe-metal organic framework (NiCe-MOF) was grown in-situ on the surface of raw wood microchannels by using abundant surface hydroxide groups. Then, this catalyst was carbonized at 600 °C in a N2 atmosphere to obtain NiCe-MOF derived catalyst/wood carbon (NiCe-MDC/WC), which was selected as a structured reactor for the steam reforming of biomass tar. NiCe-MDC/WC achieved an excellent conversion rate of approximately 99% for toluene and a high catalytic stability of 48 h at low temperature of 550 °C. Moreover, NiCe-MDC/WC showed higher catalytic performance than Ni-MDC/WC (~79%), crushed-NiCe-MDC/WC (~94%), and Ni/WC (~75%) in stability tests. These excellent results were assumed to be derived from the multilevel structure obtained from wood carbon microchannels and secondary layered MOF channels, appropriate metal-support interactions, and the presence of Ce, which could improve the dispersion of active sites and mass transfer efficiency and inhibit coke formation. Thus, such Ni-based MOF-derived structured reactors are promising for tar conversion and useful syngas production.  相似文献   

7.
This research aims to evaluate the hydrogen production and removal ability of impurity (e.g. tar and NH3) generated from sewage and textile sludge co-gasification using lab-scale fluidized-bed gasifier with an integrated hot-gas cleaning system. The gasification temperature and equivalence ratio (ER) were controlled at 850 °C and 0.2, as well as the hot gas cleaning system operated at 250 °C with the combination of zeolite, calcined dolomite, and activated carbon. Experimental results indicated that the H2 and CO yield in co-gasification of the tested sludge ranged from 2.12 to 2.45 mol/kg and from 2.83 to 3.98 mol/kg, respectively. The overall energy content of produced gas ranged between 2.40 and 2.63 MJ/kg, and cold gas efficiency (CGE) was nearly 15%. The impurities of produced gas were effectively mitigated by the hot-gas cleaning system, which could remove approximately 90% of the heavy fraction tar, up to 77% of total tar, and about 35% of ammonia. In summary, the combination of the fluidized-bed gasifier and the hot-gas cleaning system had been well developed for purifying the syngas produced from the tested sludge, and it could be applied to other organic wastes in the future.  相似文献   

8.
This paper presents the results from experimental study of syngas production by catalytic cracking of tar in wastewater under supercritical condition. Ni/Al2O3 catalysts were prepared via the ultrasonic assisted incipient wetness impregnation on activated alumina, and calcined at 600 °C for 4 h. All catalysts showed mesoporous structure with specific surface area in a range of 146.6–215.3 m2/g. The effect of Ni loading (5–30 wt%), reaction temperature (400–500 °C), and tar concentration (0.5–7 wt%) were systematically investigated. The overall reaction efficiency and the gas yields, especially for H2, were significantly enhanced with an addition of Ni/Al2O3 catalysts. With 20%Ni/Al2O3, the H2 yield increased by 146% compared to the non-catalytic experiment. It is noteworthy that the reaction at 450 °C with the addition of 20%Ni/Al2O3 had a comparable efficiency to the reaction without catalyst at 500 °C. The maximum H2 yield of 46.8 mol/kgtar was achieved with 20%Ni/Al2O3 at 500 °C and 0.5 wt% tar concentration. The catalytic performance of the catalysts gradually decreased as the reuse cycle increased, and could be recovered to 88% of the fresh catalyst after regeneration. 20%Ni/Al2O3 has a potential to improve H2 production, as well as a good reusability. Thus, it is considered a promising catalyst for energy conversion of tar in wastewater.  相似文献   

9.
The catalytic steam reforming of the major biomass tar component, toluene, was studied over two commercial Ni-based catalysts and two prepared Ru–Mn-promoted Ni-base catalysts, in the temperatures range 673–1073 K. Generally, the conversion of toluene and the H2 content in the product gas increased with temperature. A H2-rich gas was generated by the steam reforming of toluene, and the CO and CO2 contents in the product gas were reduced by the reverse Boudouard reaction. A naphtha-reforming catalyst (46-5Q) exhibited better performance in the steam reforming of toluene at temperatures over 873 K than a methane-reforming catalyst (Reformax 330). Ni/Ru–Mn/Al2O3 catalysts showed high toluene reforming performance at temperatures over 873 K. The results indicate that the observed high stability and coking resistance may be attributed to the promotional effects of Mn on the Ni/Ru–Mn/Al2O3 catalyst.  相似文献   

10.
Steel slag (SS) contains high amounts of metal oxides and could be applied as the catalyst or support material for the reforming of biomass derived tar. In this research, steel slag supported nickel catalysts were prepared by impregnation of a small amount of nickel (0–10 wt%) and calcination at 900 °C, and then tested for the catalytic reforming of biomass primary tar from pine sawdust pyrolysis. The steel slag after calcination was mainly composed of Fe2O3 and MgFe2O4, and granular NiO particles was formed and highly dispersed on the surface of nickel loaded steel slag which lead to a porous structure of the catalysts. The steel slag showed good activity on converting biomass primary tar into syngas, and its performance can be further enhanced by the loading of nickel. The yield of H2 increased significantly with the increase of nickel loading amount, while excessive nickel loading resulted in the decrease in CO and CH4 yields and significant increase in CO2 yield. The presence of steam contributed to enhancing the tar steam reforming as well as reactions between steam and produced gases, while decrease the contact probability between the reactants and the active sites of catalysts, leading to a little decrease in tar conversion efficiency but significant increase in syngas yield. The iron and nickel oxides were reduced by the syngas (CO and H2) from the biomass pyrolysis, and stable and porous structure was formed on the surface of the nickel loaded catalysts during tar reforming.  相似文献   

11.
In this study 4 different acid catalysts were prepared and mixed with commercial CZA catalysts and investigated in direct DME synthesis. Some of the used acid catalysts were not investigated in the literature therefore the work involves novelty. In a fixed-bed reactor, dimethyl ether (DME) was synthesized from the synthesis gas on two catalysts from, natural clinoptilolite and zeolite catalysts. The clinoptilolite (HK and DK) and two (HZSM5(117) and HZSM5(360)) catalysts mixed with commercial CuO/ZnO/Al2O3 (CZN) catalysts. The catalysts were also characterized by analytical chemistry techniques such as XRD, BET, TGA, and FTIR. Four different catalysts (HK, DK, HZSM5(117) and HZSM5(360)) and CZA catalysts were mixed at a ratio of 3/1, respectively, and studies were carried out in a fixed-bed reactor. Four different catalyst composition activity tests were made at temperatures 250, 275, and 300 °C. At the same time, the pressure was 30 and 40 bar and four different times (30, 60, 90, and 120 min). The composition of the gases fed to the system for DME was adjusted to N2/CO2/CO/H2 = 36/10/18/36 by volume. DME selectivity (SDME) and total carbon (XC) conversion were calculated for each condition. The experimental results showed that the highest DME selectivity of 96.50% was observed in the reaction of the DK + CZA catalyst mixture at 250 °C and 30 min at 40 bar. In addition, high DME selectivity was obtained in all reactions of DK + CZA and HK + CZA catalyst compositions at three different temperatures. The highest DME selectivity obtained is 89.69% for the reaction of the HK + CZA catalyst mixture at 300 °C and 60 min at 30 bar. Experimental results gave insights into Dimethyl ether synthesis from syngas on clinoptilolite zeolite and HZSM5-based hybrid catalysts in a fixed-bed reactor.  相似文献   

12.
For the production of bio-SNG (substitute natural gas) from syngas of biomass steam gasification, trace amounts of sulfur and tar compounds in raw syngas must be removed. In present work, biomass gasification and in-bed raw gas upgrading have been performed in a decoupled dual loop gasifier (DDLG), with aggregation-resistant nickel supported on calcined olivine (Ni/olivine) as the upgrading catalyst for simultaneous desulfurization and tar elimination of biogenous syngas. The effects of catalyst preparation, upgrading temperature and steam content of raw syngas on sulfur removal were investigated and the catalytic tar reforming at different temperatures was evaluated as well. It was found that 850 °C calcined Ni/olivine was efficient for both inorganic-sulfur (H2S) and organic-sulfur (thiophene) removal at 600–680 °C and the excellent desulfurization performance was maintained with wide range H2O content (27.0–40.7%). Meanwhile, tar was mostly eliminated and H2 content increased much in the same temperature range. The favorable results indicate that biomass gasification in DDLG with Ni/olivine as the upgrading bed material could be a promising approach to produce qualified biogenous syngas for bio-SNG production and other syngas-derived applications in electric power, heat or fuels.  相似文献   

13.
Ni-based catalysts have been widely studied in reforming methane with carbon dioxide. However, Ni-based catalysts tends to form carbon deposition at low temperatures (≤600 °C), compared with high temperatures. In this paper, a series of Ni/SiO2-XG catalysts were prepared by the glycine-assisted incipient wetness impregnation method, in which X means the molar ratio of glycine to nitrate. XRD, H2-TPR, TEM and XPS results confirmed that the addition of glycine can increase Ni dispersion and enhance the metal-support interaction. When X ≥ 0.3, these catalysts have strong metal-support interaction and small Ni particle size. The Ni/SiO2-0.7G catalyst has the best catalytic performance in dry reforming of methane (DRM) test at 600 °C, and its CH4 conversion is 3.7 times that of Ni/SiO2-0G catalyst. After 20 h reaction under high GHSV (6 × 105 ml/gcat/h), the carbon deposition of Ni/SiO2-0.7G catalyst is obviously lower than that of Ni/SiO2-0G catalyst. Glycine-assisted impregnation method can enhance the metal-support interaction and decrease the metal particle size,which is a method to prepare highly dispersed and stable Ni-based catalyst.  相似文献   

14.
《能源学会志》2020,93(3):1074-1082
A dual loop gasification system (DLG) has been previously proposed to facilitate tar destruction and H2-rich gas production in steam gasification of biomass. To sustain the process auto-thermal, however, additional fuel with higher carbon content has to be supplied. Co-gasification of biomass in conjunction with coal is a preferred option. Herein, the heat balance of the steam co-gasification of pine sawdust and Shenmu bituminous coal in the DLG has been analyzed to verify the feasibility of the process with the help of Aspen Plus. Upon which, the co-gasification experiments in the DLG have been investigated with olivine as both solid heat carriers and in-situ tar destruction catalysts. The simulation results show that the self-heating of the DLG in the co-gasification is achieved at the coal blending ratio of 28%, gasification circulation ratio of 19 and reforming circulation ratio of 20 when the gasifier temperature 800 °C, reforming temperature 850 °C, combustor temperature 920 °C and S/C 1.1. The co-gasification experiments indicate that the tar is efficiently destructed in the DLG at the optimized reformer temperature and with olivine catalysts.  相似文献   

15.
Syngas production from biomass gasification is a potentially sustainable and alternative means of conventional fuels. The current challenges for biomass gasification process are biomass storage and tar contamination in syngas. Co-gasification of two biomass and use of mineral catalysts as tar reformer in downdraft gasifier is addressed the issues. The optimized and parametric study of key parameters such as temperature, biomass blending ratio, and catalyst loading were made using Response Surface Methodology (RSM) and Artificial Neural Network (ANN) on tar reduction and syngas. The maximum H2 was produced when Portland cement used as catalyst at optimum conditions, temperature of 900 °C, catalyst-loading of 30%, and biomass blending-ratio of W52:OPF48. Higher CO was yielded from dolomite catalyst and lowest tar content obtained from limestone catalyst. Both RSM and ANN are satisfactory to validate and predict the response for each type of catalytic co-gasification of two biomass for clean syngas production.  相似文献   

16.
Steam gasification of Miscanthus X Giganteus (MXG) at high heating rate in a fluidised bed reactor with the use of olivine as catalyst was investigated. The effects of temperature (815-880 °C) on the yields and the compositions of syngas and tars were determined. The experimental results show that the gas yields and the content of H2 increase with the temperature, while the yields of tar, char and the content of CO, CO2 and CH4 in the product gas decrease. Noteworthy is that about 1.1 m3 of dry gas (at ambient conditions) per kg of dry ash free biomass were obtained with about 46% of H2 and 24% of CO by volume at 880 °C.The tars composition was determined by FTIR, NMR and GC/MS. The identification of different compounds shows mainly the presence of simple molecules. This may be facilitating the possibility of complete tar reforming process (hot gas cleaning), to improvement of the syngas yield and the decrease of the formation of pollutants.  相似文献   

17.
The self-regeneration of Ni-based catalysts has been considered as a promising approach to maintain not only a continuous but also economical process. However, the effect of catalyst nature, operating temperature, amount and types of carbon deposits on the effectiveness of the in-situ regeneration is still not well-investigated. Therefore, in this work, the self-regeneration ability of the undoped and Dy-doped Ni/SiO2 catalysts, which were prepared by the same impregnation method, were examined in the dry reforming of methanol. The physicochemical properties of the fresh and spent catalysts were analyzed by various techniques such as X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H2-TPR), oxygen temperature-programmed desorption (O2-TPD), transmission electron microscopy (TEM), N2-BET isothermal adsorption. The nature and chemical reactivity of coke deposits formed during dry reforming at various temperatures (550, 600, and 650 °C) and the regeneration possibility of used catalysts through CO2 gasification at these temperatures were investigated by the in-situ temperature-programmed gasification by CO2 (TPCO2). The Dy additive significantly improves the dispersion of the nickel active sites of Ni/SiO2 catalyst, as demonstrated by the decreased Ni crystal size as well as the increased specific surface area and reduction degree of the catalyst. Furthermore, Dy promotion increases the quantity of oxygen vacancies and the nature of oxygen species, thereby improving the catalyst activity and stability. Specifically, methanol conversion dropped from 93% to 96%–61% and 31% for undoped Ni/SiO2 at 600 °C and 650 °C, respectively and from about 99% to 87% (at 600 °C) and 52% (at 650 °C) for Dy-doped catalyst.  相似文献   

18.
To produce the high quality H2-rich syngas from biomass and plastic wastes, a two-stage pyrolysis-gasification system involving pyrolysis and catalytic gasification is considered as a suitable route. Generally, synthesis of highly active, low cost and coke-resistant catalyst for tar cracking is the key factor. A series of monometallic catalysts of Ni@CNF/PCs and Fe@CNF/PCs and the bimetallic Ni–Fe@CNF/PCs catalyst were prepared by a simple one-step pyrolysis approach for high quality syngas production from pyrolysis-gasification of biomass and plastic wastes. The results indicated that the bimetallic Ni–Fe@CNF/PCs catalyst appeared as the optimal catalyst in affording the best compromise between catalytic activity and stability with the existence of the excellent dispersibility of the Fe0.64Ni0.36 alloy nanoparticles and the carbon nanofibers/porous carbon composite structure. In addition, the optimal operation conditions of biomass/plastic ratio of 1/2 and gasification temperature of 700 °C were observed for the bimetallic Ni–Fe@CNF/PCs catalyst to play best roles in the H2-rich syngas quality, with up to 33.66 mmol H2/g biomass, and tar yields as low as 5.66 mg/g.  相似文献   

19.
In this work, a sol-gel Ni–Mo2C–Al2O3 catalyst is employed for the first time in the glycerol steam reforming for syngas production. Catalyst stability and activity are investigated in the temperature range of 550 °C–700 °C and time on stream up to 30 h. As reaction temperature increases, from 550 °C to 700 °C, H2 yield boosts from 22% to 60%. The stability test, carried out at milder conditions (600 °C and Gas-Hourly Space-Velocity (GHSV) of 50,000 mL h−1.gcat−1), shows high catalyst stability, up to 30 h, with final conversion, H2 yield, and H2/CO ratio of 95%, 53% and 1.95, respectively. Both virgin and spent catalysts have been characterized by a multitude of techniques, e.g., Atomic-Absorption spectroscopy, Raman spectroscopy, N2-adsorption-desorption, and Transmission Electron Microscopy (TEM), among others. Regarding the spent catalysts, carbon deposits’ morphology becomes more graphitic as the reaction temperature increases, and the total coke formation is mitigated by increasing reaction temperature and lowering GHSV.  相似文献   

20.
Natural Egyptian bentonite clay intercalated with both La and Ni having different molar ratio (La: Ni = 2:1, 1:1 & 1:2) were prepared, saving 5mmole pillar/gm clay, using ultrasonic assistance method. The prepared catalysts were calcined at 450 and then reduced at 400 °C & 600 °C.Characterization of the prepared LaNi-PILC was achieved by X-ray diffraction (XRD), Furrier transform infrared spectroscopy (FTIR), N2 adsorption desorption isotherm (BET) and H2-temperature programmed reduction (H2-TPR). The data confirm the success of intercalation process for both La & Ni in the lamellar structure of bentonite clay. The La: Ni molar ratio affected the specific surface area, Ni crystal size, dispersion and reducibility of the prepared catalyst. The reduction temperature had a great effect on the reactivity and product selectivity during CO2/CH4 reforming at different reaction temperatures (600–800 °C). Where, reduction at 400 °C gives rise to CH4 oxidation reaction (MOR) with formaldehyde as a main product. While reduction at 600 °C enhances the activity and stability for CO2 reforming of methane (CRM) and syngas production (H2/CO ~ 1.19). The most active and stable LaNi1:2-PILC5 catalyst (CO2 and CH4 conversions reached 85% and 90% respectively) is superior with respect to the performance of PILC based catalysts reported in the literatures.  相似文献   

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