玉米秸秆催化热解制取富氢气体

文章利用管式炉反应器研究了12种催化剂对玉米秸秆热解制取富氢气体的影响,并结合气相、固相、液相产物的特性以及催化剂表征探究了物质的迁移转化规律。研究结果表明：添加10%Ni/CaO-sg的实验组达到了最佳效果,热解气产率从无催化热解时的27.8%提升至46.5%,H₂产量从53.7 mL/g上升至142.0 mL/g,H₂所占比例也从24.2%上升至32.1%;在CaO主剂的催化作用下,原料的无序性热解反应进行得更加充分,热解炭产率降低,进而在负载镍的10%Ni/CaO-sg催化作用下,热解油中的重组分芳香烃类化合物裂解成较轻的酚类,同时烷烃和烯烃含量增多,这些反应均促使热解气产率增加及氢气产量的提升。     

生物质二次裂解制取氢气的研究

采用生物质热解及二次裂解的方法制取富氢气体.通过对生物质热解产生的气液体成份进行二次裂解,实现热解组分中焦油等含氢化合物的深度转化,提高产品气体中氢气的含量,同时解决了热解产品气中焦油不易去除的难题,得到洁净的富氢气体.实验选用稻壳为原料,分析了热解温度和物料滞留时间等因素对热解气体成份的影响,比较了热解气体和二次裂解气体成份的变化,同时分析了水蒸汽、催化剂等因素对裂解气体成份的影响.实验结果表明,热解温度和物料滞留时间的增加提高了热解气体中氢气的含量,二次裂解、水蒸汽和催化剂的引入都能在一定程度上提高产品气中H2的含量.实验最终表明,氢气体积含量可达到60%以上.     

湿牛粪催化热解制取富氢气体

以SiO_2、CaO、牛粪灰以及K_2CO_3为催化剂,对湿牛粪进行热解气化制富氢气体的试验研究。结果表明,各催化剂对牛粪热裂解反应催化作用的强弱顺序依次为K_2CO_3牛粪灰CaOSiO_2。在催化反应过程中,SiO_2的催化方向是牛粪热解液化产焦油方向而非热解气化产热解气方向,CaO对牛粪热解产焦油和产热解气均具有较好的催化作用,牛粪灰的催化作用主要表现在焦炭与水蒸气的蒸汽重整反应上,而K_2CO_3主要表现在焦油的二次裂解与蒸汽重整反应上。从经济成本与催化效果角度综合考量,牛粪灰催化湿牛粪热解制取富氢气体具有良好的实际应用价值。     

生物质气化制氢的模拟

以秸秆为研究对象,利用Aspen P lus软件建立气化反应器模型,对生物质气化制氢进行模拟计算.探讨不同反应条件,包括气化温度、生物质与蒸汽质量配比以及催化剂对富氢气体成分的影响.计算结果表明,未加催化剂条件下,采用生物质蒸汽气化技术可获得体积分数为6000/以上的富氢燃料气,增大蒸汽与生物质质量配比有利于氢气产率的提高;添加CaO、MgO催化剂可较大幅度地提高氢气产率,氢气体积分数最大可达到9400/,其中CaO对生物质气化制氢过程的催化作用非常显著.     

生物质二级固定床催化热解制取富氢燃气

针对二级固定床反应器(第一级是热解反应器,第二级是催化反应器),以制取富氢燃气为目标,分别采用稻壳、秸秆、锯末为原料,重点考察了固定床催化反应器在不同反应条件下对产气量、产氢率和焦油含量的影响.与一级热解反应相比,在催化反应器温度为750℃时,稻壳热解的产气量提高了22%,氢气的体积含量提高了50.3%;通过使用煅烧白云石和镍基催化剂,稻壳热解的产气量提高了36.6%,氢气的体积含量提高了76.2%.催化反应器温度为815℃时,秸秆和锯末的热解实验结果与温度为750℃时具有相同的趋势,且催化固定床能够有效降低燃气中焦油的含量,可降至原来含量的1%.催化剂负载量和燃气空速对产气量和氢气浓度都有影响.催化剂负载量为生物质送料量的30%、燃气空速为0.9×104h-1时,实验结果相当满意.     

核桃壳与花生壳催化热解制氢的动力学研究

利用自制的热解反应炉,选取核桃壳与花生壳作为试验原料,以MnO2、Al2O3、CaO 3种金属氧化物为催化剂,进行了一系列催化热解制备氢气的研究.实验中着重对比研究了催化剂存在的情况下,两种原料热解时活化能的变化规律.分析了不同催化剂使用量对实验结果的影响,计算了物料催化热解制的反应动力学参数.结果表明,选择适宜的催化剂,可以提高果壳类废弃物热解过程的气相产率,同时能够降低反应活化能,使热解过程更加易于进行.     

稻草催化热解制取氢气的研究

利用自制的热解反应炉,选取陕西汉中稻草为原料,以MnO2、Al2O3、MgO这3种金属氧化物为催化剂,进行了一系列催化热解制备氢气的研究,并采用气相色谱对氢气进行分析.实验着重研究了不同催化剂以及不同催化剂添加量对氢气浓度和产量的影响.结果表明:添加0.1%的Al2O3、MgO、MnO2作为催化剂,各个温度段的氢气产量均有不同程度的提高,催化活性为氧化镁>氧化铝>氧化锰,催化剂的添加量对于稻草热解产氢的浓度和产量也有直接影响.     

生物质流化床催化气化制取富氢燃气

以流化床和固定床为反应器，以制取富氢燃气为目标，对生物质催化气化进行了研究。实验所用催化剂为白云石和镍基催化剂。白云石作为流态化催化剂在流化床内使用；镍基催化剂在流化床出口的固定床反应器内使用。重点研究了不同固定床反应条件对气体和氢产率的影响。固定床反应条件为：温度，650～850℃，催化剂质量空速，2．68～10．72h^-1。在催化反应器出口，H2体积平均含量超过50％，CH4含量降低50％左右，C2组分降低到1％以下。在实验条件范围内，最高气体产率可以达到3．31Nm^3／kg biomass，最高氢产率可达到130．28g H2／kg biomass，对镍基催化剂350min的寿命测试表明，该系统具有较稳定的操作性能。     

基于氯化镁的石油焦-水蒸气气化过程影响因素分析

以石油焦为气化原料、以氯化镁为催化剂制取氢气,基于Aspen Plus模拟软件建立石油焦-水蒸气气化模型,在验证模型的基础上,进行气化过程的模拟仿真计算,分析不同条件下(气化温度、气化压力、催化剂添加量、H_2O/PC质量比)对石油焦气化制备富氢气体的热力学影响。H_2、CO、CO_2的模拟值与实验值吻合较好,说明此模型具有一定的适用性。结果表明:升高温度会使氢气的体积分数降低,石油焦-水蒸气制富氢气体最适宜温度为700℃;增大压力会使氢气的体积分数降低,石油焦-水蒸气制富氢气体最适宜压力为0.1MPa;增大H2O/PC质量比可以使H_2的体积分数上升,当H_2O/PC质量比为6时,上升趋势变缓,因此石油焦-水蒸气制富氢气体最适宜水蒸气质量流量为石油焦的6倍;随着催化剂氯化镁添加量的增多,H_2的体积分数也会上升,当氯化镁添加量为5%时,H_2体积分数提高4%。     

氢氧化钾催化木屑热解特性影响研究

为了考察钾盐催化剂对生物质热解特性的影响,实验以木屑为原料,采用浸渍方法加入不同质量KOH,干燥和粉碎后进行热重和热解实验。实验中使用热重分析仪对样品进行热重实验,采用Starink法进行动力学分析,使用自行搭建的固定床热解炉研究热解温度和KOH添加量对木屑热解的影响。热重结果表明,加入KOH后热解温度降低,改变了木屑热解路径,降低了热解失重速率。动力学分析结果表明,加入KOH后使木屑主要热解区间表观活化能降低。热解实验结果表明,加入KOH后,木屑热解产物中热解油产率降低,热解合成气和半焦产率增加。热解产物经分析发现,加入KOH后,热解合成气中氢气含量显著增加,热解油品质有所改善,低KOH添加量对半焦孔隙结构影响较小,高KOH添加量使半焦的孔隙更加发达。     

Novel hydrogen‐rich gas production by steam gasification of biomass in a research‐scale rotary tubular helical coil gasifier

The concept of biomass steam gasification offers platform for production (i) of hydrogen, (ii) hydrocarbons and (iii) value added chemicals. Majority of these developments are either in nascent or in pilot/demonstration stage. In this context, there exists potential for hydrogen production via biomass steam gasification. Gaseous products of biomass steam gasification consist of large percentage of CO, CH₄ and other hydrocarbons, which can be converted to hydrogen through water‐gas‐shift reaction, steam reforming and cracking respectively. Although there are many previous research works showing the potential of production of hydrogen from biomass in a two stage process, challenges remain in extended biomass and char gasification so as to reduce the amount of carbon in the residual char as well as improve conversion of heavy hydrocarbon condensates to hydrogen rich gas. In the current work, the characteristics of biomass steam gasification in an in‐house designed rotary tubular helical coil reactor at temperatures less than 850 °C, in the presence of superheated steam, were presented. The objectives were to obtain high carbon conversion in the primary biomass steam gasification step (upstream) and high product gas yield and hydrogen yield in the secondary fixed bed catalytic step (downstream). The influence of temperature, steam‐to‐biomass ratio and residence time on product gas yield in the rotary tubular helical coil gasifier was studied in detail using one of the abundantly available biomass sources in India‐rice husk. Further, enhancement of product gas yield and hydrogen yield in a fixed bed catalytic converter was studied and optimized. In the integrated pathway, a maximum gas yield of 1.92 Nm³/kg moisture‐free biomass was obtained at a carbon conversion efficiency of 92%. The maximum hydrogen purity achieved under steady state conditions was 53% by volume with a hydrogen yield of 91.5 g/kg of moisture‐free biomass. This study substantiates overall feasibility of production of high value hydrogen from locally available biomass by superheated steam gasification followed by catalytic conversion. Copyright © 2016 John Wiley & Sons, Ltd.     

Hydrogen-rich gas production by steam gasification of palm oil wastes over supported tri-metallic catalyst

The catalytic steam gasification of palm oil wastes for hydrogen-rich gas production was experimentally investigated in a combined fixed bed reactor using the newly developed tri-metallic catalyst. The results indicated that the supported tri-metallic catalyst had greater activity for the cracking of hydrocarbons and tar in vapor phase and higher hydrogen yield than the calcined dolomite in catalytic steam gasification of palm oil wastes. A series of experiments have been performed to explore the effects of temperature, steam to biomass ratio (S/B) and biomass particle size on gas composition, gas yield, low heating value (LHV) and hydrogen yield. The experiments demonstrated that temperature was the most important factor in this process; higher temperature contributed to higher hydrogen production and gas yield, however, it lowered gas heating value. Comparing with biomass catalytic gasification, the introduction of steam improved gas quality and yield, the optimal value of S/B was found to be 1.33 under the present operating condition. It was also shown that a smaller particle size was more favorable for gas quality and yield. However, the LHV of fuel gas decreased with the increasing S/B ratio and the decreasing biomass particle size.     

Hydrogen-rich gas production from biomass steam gasification in an updraft fixed-bed gasifier combined with a porous ceramic reformer

This paper investigates the hydrogen-rich gas produced from biomass employing an updraft gasifier with a continuous biomass feeder. A porous ceramic reformer was combined with the gasifier for producer gas reforming. The effects of gasifier temperature, equivalence ratio (ER), steam to biomass ratio (S/B), and porous ceramic reforming on the gas characteristic parameters (composition, density, yield, low heating value, and residence time, etc.) were investigated. The results show that hydrogen-rich syngas with a high calorific value was produced, in the range of 8.10–13.40 MJ/Nm³, and the hydrogen yield was in the range of 45.05–135.40 g H₂/kg biomass. A higher temperature favors the hydrogen production. With the increasing gasifier temperature varying from 800 to 950 °C, the hydrogen yield increased from 74.84 to 135.4 g H₂/kg biomass. The low heating values first increased and then decreased with the increased ER from 0 to 0.3. A steam/biomass ratio of 2.05 was found as the optimum in the all steam gasification runs. The effect of porous ceramic reforming showed the water-soluble tar produced in the porous ceramic reforming, the conversion ratio of total organic carbon (TOC) contents is between 22.61% and 50.23%, and the hydrogen concentration obviously higher than that without porous ceramic reforming.     

Hydrogen-rich gas production by air–steam gasification of rice husk using supported nano-NiO/γ-Al2O3 catalyst

The air–steam catalytic gasification of rice husk for hydrogen-rich gas production was experimentally investigated in a combined fixed bed reactor with the newly developed nano-NiO/γ-Al₂O₃ catalyst. A series of experiments have been performed to explore the effects of catalyst presence, catalytic reactor temperature, the equivalence ratio (ER), and steam to biomass ratio (S/B) on the composition and yield of gasification gases. The experiments demonstrated that the developed nano-NiO/γ-Al₂O₃ catalyst had a high activity of cracking tar and hydrocarbons, upgrading the gas quality, as well as yielding a high hydrogen production. Catalytic temperature was crucial for the overall gasification process, a higher temperature contributed to more hydrogen production and gas yield. Varying ER demonstrated complex effects on rice husk gasification and an optimal value of 0.22 was found in the present study. Compared with biomass catalytic gasification under air only, the introduction of steam improved the gas quality and yield. The steam/biomass ratio of 1.33 was found as the optimum operating condition in the air–steam catalytic gasification.     

Integrated catalytic adsorption (ICA) steam gasification system for enhanced hydrogen production using palm kernel shell

This paper investigates the integrated catalytic adsorption (ICA) steam gasification of palm kernel shell for hydrogen rich gas production using pilot scale fluidized bed gasifier under atmospheric condition. The effect of temperature (600–750 °C) and steam to biomass ratio (1.5–2.5 wt/wt) on hydrogen (H₂) yield, product gas composition, gas yield, char yield, gasification and carbon conversion efficiency, and lower heating values are studied. The results show that H₂ hydrogen composition of 82.11 vol% is achieved at temperature of 675 °C, and negligible carbon dioxide (CO₂) composition is observed at 600 °C and 675 °C at a constant steam to biomass ratio of 2.0 wt/wt. In addition, maximum H₂ yield of 150 g/kg biomass is observed at 750 °C and at steam to biomass ratio of 2.0 wt/wt. A good heating value of product gas which is 14.37 MJ/Nm³ is obtained at 600 °C and steam to biomass ratio of 2.0 wt/wt. Temperature and steam to biomass ratio both enhanced H₂ yield but temperature is the most influential factor. Utilization of adsorbent and catalyst produced higher H₂ composition, yield and gas heating values as demonstrated by biomass catalytic steam gasification and steam gasification with in situ CO₂ adsorbent.     

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen. However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/N m³ for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H₂/kg biomass. For biomass oxygen/steam gasification, the content of H₂ and CO reaches 63.27–72.56%, while the content of H₂ and CO gets to 52.19–63.31% for biomass air gasification. The ratio of H₂/CO for biomass oxygen/steam gasification reaches 0.70–0.90, which is lower than that of biomass air gasification, 1.06–1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.     

Hydrogen production from oil sludge gasification/biomass mixtures and potential use in hydrotreatment processes

Gasification of oil sludge (OS) from crude oil refinery and biomass was investigated to evaluate hydrogen production and its potential use in diesel oil hydrodesulphurization process. Gasification process was studied by Aspen Hysys^® tools, considering different kinetic model for main OS compounds. Air and superheated steam mixtures as gasifying agents were simulated. Gasification parameters like: temperature, syngas chemical composition and gas yield were evaluated. Results showed OS thermal conversion needs a working temperature above 1300 °C to ensure a high conversion (>90%) of OS compounds. Thermal energy requirement for gasification was estimated between 0.80 and 1.25 kWh/kg OS, considering equivalence air (ER) and steam/oil sludge (SOS) ratio between 0.25-0.37 and 0.2–1.5 kg steam/kg OS, respectively. The gas yield was 2.28 Nm³/kg OS, with a H₂ content close to 25 mol%, for a H₂ potential production about 1.84 Nm³ H₂/kg OS; nevertheless, when OS and biomass mixtures are used, hydrogen production increases to 3.51 Nm³ H₂/kg OS, meaning 37% of H₂ (from natural gas) required for diesel oil hydrodesulphurization could be replaced, becoming an added value technological alternative for OS waste conversion as a source of H₂, inducing a considerable reduction of greenhouse gases and non-renewables resources.     

Oxidative catalytic steam gasification of sugarcane bagasse for hydrogen rich syngas production

Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al₂O₃ catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al₂O₃ performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H₂/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.     

Integrated adsorption steam gasification for enhanced hydrogen production from palm waste at bench scale plant

The generation of hydrogen-enriched synthesis gas from catalytic steam gasification of biomass with in-situ CO₂ capture utilizing CaO has a high perspective as clean energy fuels. The present study focused on the process modeling of catalytic steam gasification of biomass using palm empty fruit bunch (EFB) as biomass for hydrogen generation through experimental work. Experiment work has been carried out using a fluidized bed gasifier on a bench-scale plant. The established model integrates the kinetics of EFB catalytic steam gasification reactions, in-situ capturing of CO₂, mass and energy balance calculations. Chemical reaction constants have been calculated via the parameters fitting optimization approach. The influence of operating parameters, mainly temperature, steam to biomass, and sorbent to biomass ratio, was investigated for the hydrogen purity and yield through the experimental study and developed model. The results predicted approximately 75 vol% of the hydrogen purity in the product gas composition. The maximum H₂ yield produced from the gasifier was 127 gH₂/kg of EFB via experimental setup. The increase in both steam to biomass ratio and temperature enhanced the production of hydrogen gas. Comparing the results with already published literature showed that the current system enables to produce a high amount of hydrogen from EFB.