生物质热解气化制取氢气

该文对生物质的热化学方法(主要是气化和热解)制取氢气进行了归纳总结，在此基础上研究了用热解方法从生物质原料中制取氢气的技术路线并介绍了催化制氢的实验室研究结果。研究的结果表明：催化剂的添加对热解过程的最终产品气及富氢气体的产率有影响；催化剂的负荷量对富氢气体的产率有显著影响，其值存在一个优化范围；同样的催化剂对稻杆和锯末热解获得的富氢气体的产率影响不同。     

双流化床生物质气化及CO2捕获的模拟

用Aspen Plus建立了双流化床气化和燃烧模型,对生物质在双流化床中气化及CaO吸收合成气中的CO2过程进行了模拟研究;探讨不同反应条件:气化温度、蒸汽与生物质的质量配比(S/B)以及CaO循环量与生物质的质量配比(Ca/B)对合成气成分的影响,为该类型工业反应器的研发提供了理论依据.模拟分析结果表明:气化温度低于700℃时,CaO能很好地吸收气化过程中产生的CO2并促进平衡反应向产氢方向进行;在温度为650℃及CaO作用下,S/B在0.6～1.7内对合成气成分的影响不大;CaO的加入能够有效地改善合成气的组成,合成气中氢气浓度能达到95％以上,氢气产量达到52 mol/kg.     

CaO吸附作用对石油焦-水蒸气气化的热力学分析

为提高石油焦气化产氢率与产甲烷率,基于Aspen plus软件建立石油焦-水蒸气气化模型,并引入氧化钙添加剂,研究气化温度、压力、CaO/石油焦质量比、H_2O/石油焦质量比对石油焦气化制取富氢气体与富甲烷气体的影响。结果表明,将氧化钙引入石油焦气化系统可以有效提高氢气和甲烷的体积分数,当CaO/石油焦质量比为3时氢气的体积分数可提高20个百分点,当CaO/石油焦质量比为1时甲烷的体积分数可提高15个百分点;增大水蒸气流量有利于制备富氢气体,而不利于制备富甲烷气体,石油焦气化制取甲烷的水蒸气最佳添加量为H_2O/石油焦质量比为1,制取氢气的水蒸气最佳添加量为H_2O/石油焦质量比为10;低温低压有利于制备富氢气体,石油焦-CaO气化制氢的最适宜温度为600~650℃,最适宜压力为0.1MPa;低温高压有利于制备富甲烷气体,石油焦-CaO气化制甲烷的最适宜温度为600~750℃,最适宜压力为1MPa。     

纤维素废弃物稀酸水解残渣制氢研究

对纤维素废弃物水解残渣催化气化制氢进行了研究,考察了气化温度、催化温度、催化剂颗粒粒径和S/B (单位时间内进入气化器中水蒸汽质量与生物质质量之比)4个主要参数对气体组成和氢气产率的影响并和以木屑为原料催化气化制氢进行了比较。在试验范围内提高气化温度、催化温度和S/B的值以及减小催化剂颗粒粒径对提高氢产率有利,其中气化温度和S/B对提高氢产率影响较大。气化温度在800～850℃内较为理想,催化剂颗粒的适宜粒径为2～3mm,S/B取1.5～2.0较佳;和木屑制氢相比,使用水解残渣制取的气体中CO和CO_2的体积百分比小,H_2/CO的值大,氢气含量高,有利于后续处理,且氢产率大,对制氢有利。     

生物质/甘油共气化制氢实验研究

以水蒸气为气化介质,在固定床实验台上进行生物质/甘油共气化制氢实验研究。实验考察给水速度、Ca O、压力、催化剂对制氢结果的影响,结果表明:由于Ca O的存在,给水速度对氢气浓度的影响呈曲线变化。提高Ca O的含量能明显促进氢气的产生;压力的升高促进共气化向制氢方向的进行,这与压力对生物质、甘油单独气化的影响截然相反;镍基催化剂的使用存在最佳值,过量催化剂会抑制制氢反应的进行。     

串行流化床生物质气化制取富氢气体模拟研究

利用串行流化床技术将生物质热解气化和燃烧过程分开,气化反应器和燃烧反应器之间通过灰渣进行热量传递,实现了自供热下生物质气化制氢.利用Aapen Plus软件模拟制氢过程,通过比较单反应器生物质气化的模拟结果和实验结果,验证了模拟研究的可行性.重点研究串行流化床中非催化气化与CaCO3作用下的气化过程,探讨了气化温度、蒸汽与生物质的质量配比(S/B)对制氢的影响,为今后开展生物质气化制氢试验提供了理论参考.结果表明:对应不同气化温度,S/B都存在一个最佳值,且随着温度升高其值减小.当气化温度低于750℃时,添加CaCO3可大幅提高氢产率,气化温度为700℃且在S/B约为0.9时氢产率最大,达43.7 mol·(kg生物质)-1(干燥无灰基),比同温度下非催化气化提高了20.3%.随着气化温度升高,CaCO3促进作用减弱.     

基于ASPEN PLUS模拟生物质与煤气流床共气化工艺

基于ASPEN PLUS软件模拟平台,对生物质与煤气流床共气化过程进行模拟,考察操作条件及生物质与煤配比变化对气化性能的影响。模拟计算结果表明:与生物质单独气化相比,生物质与煤共气化能提高气化温度及气化效率;与煤单独气化相比,生物质可部分替代煤且不会明显改变气化效果,尽管气化温度略有下降,但混合物灰熔点的降低能很好弥补这一变化。生物质质量分数为20%,[O]/[C]摩尔比在1.1～1.3时气化效果最佳,气化温度约为1250℃,有效气产率1.92Nm~3/kg,煤气热值可达到11.5MJ/Nm~3,冷煤气效率79.7%。     

生物质炭催化裂解焦油的实验研究

通过实验方法研究了生物质炭对生物质热解焦油的催化特性。通过分析焦油裂解率在催化剂及其重量、蒸汽加入量和加入方式、氮气流量等条件下的变化可知:在蒸汽条件下,生物质炭对焦油有显著的催化裂解效果,最高焦油转化率可达96.1%。通过对实验条件下裂解产物、裂解气体积分数的分析可知,生物质炭和蒸汽可以促进热解产物里面的可凝结相转化为不可凝结的气体,并且导致气体组分体积分数的变化。裂解气中氢气产量增加较快,最高可达裂解气体积的50.2%。     

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%。     

生物质催化气化制取富氢气体实验研究

以麦秸为对象,采用管式气化炉进行生物质蒸汽气化制取富氢气体实验研究.在非催化气化实验基础上,选取NiO、纯Fe粉以及橄榄石(FeMg)2:SiO4这3类催化剂来提高氢含量.实验结果表明,气化反应温度在700～950℃范围内,氢体积浓度达到45%以上,添加Fe时达到了60%以上.非催化时,氢产率达到60g/(kg麦秸);添加催化剂时,Fe粉催化效果最好,最大产氢率达到119g/(kg麦秸);NiO次之,相比非催化时可提高40%;而橄榄石催化作用明显低于前两者.另外随着气化温度提高,3种催化剂的催化作用均增强.     

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.     

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 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 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.     

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 energy production from disposable chopsticks by a low temperature catalytic gasification

This study investigates the comparison of various mineral catalysts on the enhancement of energy yield efficiency with low temperature catalytic gasification of disposable chopsticks. The experiments were carried out in a fluidized bed reactor by controlling the temperature and keeping it within the range of 600 °C–800 °C. The mineral catalysts, such as aluminum silicate, zeolite and calcium oxide (CaO) were used as the experimental catalysts for enhancing energy yield in this research. According to the experimental results, the gasification temperature is a critical factor for improving the gas yield and quality. In general, a higher temperature provides more favorable conditions for thermal cracking and enhances the gas yield and quality. The hydrogen content produced from the tested biomass gasification by various catalysts slightly increased from 11.77% to 14.57%. Furthermore, the lower heating value of synthesis gas increased from 9.28 MJ/Nm³ to 9.62 MJ/Nm³, when the fluidized bed reactor temperature operated at 600 °C and the tested catalysts addition. That is, the catalytic gasification has good energy yield performance for enhancing higher energy content of synthesis gas in a lower-temperature catalytic fluidized bed reactor. Compared with the hydrogen production efficiency, the addition of a calcium based catalyst can reduce bed agglomeration tendency, but it also improves the energy yield in this research.     

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.     

Exergy analysis of hydrogen production from biomass gasification

For a given set of operating conditions, the hydrogen production from biomass gasification can be improved through optimization of the operating parameters and efficiencies. The present approach can predict hydrogen production via biomass gasification in a range of 10–32 kg/s from biomass (sawdust wood). The biomass is introduced to a gasifier at an operating temperature range of 1000–1500 K. Also, 4.5 kg/s of steam at 500 K is used as gasification medium. Results indicate that improvement in hydrogen production from biomass steam gasification depending on the amount of steam and quantity of biomass feeding to the gasifier as well the operating temperature. Over the range of feeding biomass, the hydrogen yield reaches 80–130 g H₂/kg biomass while in the operating temperature examined, the hydrogen yield reaches 80 g H₂/kg biomass. On mole basis it is found that, in the first range of H₂ varies from 51 to 63% in the studied range of feeding biomass in existing 4.5 kg/s from steam while H₂ gets to 51–53% in existing of 6.3 kg/s from steam.     

Influence of catalyst and temperature on gasification performance of pig compost for hydrogen-rich gas production

The catalytic steam gasification of pig compost (PC) for hydrogen-rich gas production was conducted in a fixed-bed reactor. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 700–850 °C, for weight hourly space velocity (WHSV) in the range of 0.30–0.60 h⁻¹. The results indicate that the developed NiO on modified dolomite (NiO/MD) catalyst reveals better catalytic performance on the tar elimination and hydrogen yield than calcined MD or NiO/γ-Al₂O₃ catalyst. Meanwhile, the lower WHSV and higher reactor temperature can contribute to more hydrogen production and gas yield. Moreover, the char from catalytic steam gasification of PC has a highest ash content of 75.84% at 850 °C. In conclusion, pig compost is a potential candidate for hydrogen gas production through catalytic steam gasification technology.     

生物质富氧——水蒸气气化制氢特性研究

以一个鼓泡流化床为反应器,对生物质富氧—水蒸气气化制取富氢燃气的特性进行了一系列的实验研究。通过对试验数据的分析,探讨了主要参数温度、水蒸气/生物质(S/B)和氧浓度对气体成分、氢产率和潜在产氢量的影响。结果表明:在3个主要参数的变化范围内,氢产率和潜在氢产量受温度的影响最大:当温度从700~900℃时,每千克生物质氢产量从18g增加到了53g,每千克生物质潜在氢产量从71.6g增加到了115.6g。