生物质快速裂解油水蒸气催化重整制氢研究进展

可再生的氢能源作为化石资源的替代品是一个非常重要的途径,水蒸气催化重整生物质快速裂解获得的液体产物生物油是一种可行的制取可再生氢气的过程.本文介绍了生物油水蒸气催化重整反应机理与热力学分析,介绍了催化重整制氢过程催化剂、制氢工艺条件、代表性的反应器及工艺流程.指出水蒸气催化重整生物油制氢反应的主要约束条件是由于碳的沉积导致的催化剂失活.研究开发具有高活性、高选择性,寿命长、机械强度高容易再生的催化剂与制氢反应器是当前及今后研究的重要方向.     

生物油水蒸气催化重整制氢研究进展

氢气作为重要的清洁能源和化工原料,目前主要来源于化石燃料,而生物质经快速热解制得生物油用于水蒸气催化重整制氢被认为是一种高效、环保、经济的可再生能源制氢途径。本文首先综述了近年来生物油水蒸气催化重整制氢相关反应原料;然后重点讨论了生物油水蒸气催化重整反应催化剂研究近况;总结了生物油水蒸气重整反应机理与动力学分析;最后列举了重整反应器等方面的研究进展。相比于生物油,生物油模型化合物因结构简单、转化率与氢气收率高,得到广泛研究;以Ni为代表的活性金属组分催化活性高,金属间协同作用强;不同类型的载体可增强催化剂的稳定性,碱性载体还可吸收CO₂、提高催化剂抗积炭、防烧结等方面的性能;不同结构的反应器在性能方面表现各异,主要以固定床反应器为主。研制高活性、稳定性强的催化剂,提高重整反应的循环稳定性,并总结最符合动力学规律的反应机理,以及研发高效的反应器是今后生物油水蒸气催化重整制氢研究的重点。     

生物油水蒸气催化重整制氢研究进展

生物油催化重整制氢是生物质转化为高品位能源的主要发展方向之一,引起了国内外的广泛关注。本文主要介绍了国内外生物油制取氢气的工艺、催化剂制备等技术。作者建议开发生物油流化床催化重整制氢技术和开发高效耐磨催化剂等,从而降低生物油制氢的成本。     

重整催化剂积碳失活研究进展

积碳是重整催化剂失活的重要原因,针对这一问题,综述了重整催化剂失活过程中,积碳在金属和载体的沉积情况,积碳前驱物在积碳形成中的作用,介绍了研究催化剂表面积碳形态及类型的表征手段,论述了影响重整催化剂积碳失活的因素。     

甲醇水蒸气催化重整制氢技术研究进展

针对甲醇水蒸气催化重整制氢的应用背景,综述了甲醇水蒸气重整制氢的反应机理和动力学,对用于该反应的催化剂进行了总结分类,阐述了催化剂制备和反应阶段相关因素对催化剂特性的影响。在此基础上,指出甲醇水蒸气重整制氢技术研究与应用存在的问题与瓶颈,并对两种创新的研究--太阳能驱动的甲醇水蒸气重整制氢技术和甲醇重整制氢微通道反应器的开发技术进行了总结展望。     

乙酸蒸汽催化重整制氢的研究进展

通过生物油蒸汽重整制备氢气可以减少环境污染,降低对化石燃料的依赖,是一种极具潜力的制氢途径。乙酸是生物油的主要成分之一,常作为模型化合物进行研究。镍基催化剂是乙酸蒸汽重整过程中常用的催化剂,但容易因积炭失去活性,降低了制氢过程的经济性。本文首先分析了影响乙酸蒸汽重整制氢过程的各种因素,阐述了在这一过程中镍基催化剂的积炭原理,讨论了优化镍基催化剂的方法,包括优化催化剂的预处理过程、添加助剂和选择合适的载体,最后对乙酸蒸汽重整制氢的热力学分析研究进展进行了总结。未来应重点研究多种助剂复合使用时对镍基催化剂积炭与活性的影响,分析多种助剂的协同作用机理,得到一种高活性、高抗积炭能力的用于生物油蒸汽重整制氢的镍基催化剂。     

甲烷二氧化碳催化重整制合成气的研究进展和工艺技术

近几年随着我国科学技术和经济水平的不断发展和提升,随之而来的环境问题也日益严峻,而二氧化碳则是重要的一环,为此我国政府以及相关工作部门加强了对甲烷和二氧化碳催化重整制合成气的研究力度。在甲烷和二氧化碳催化重整的相关技术取得阶段成果的同时,在反应时涉及的难点部分:催化剂的活性组分、载体的研究以及助剂的研究取得了突破,这体现出对工业发展质量和速度的高度肯定,但重整过程中仍然存在催化剂积碳失活等问题。主要对重整过程进行了综述,对重整过程需要的催化剂活性组分、载体以及催化剂积碳行为进行了介绍,并对制备方法进行了讨论。     

汽油氧化重整制氢反应催化剂失活因素研究

对汽油氧化重整制氢反应催化剂失活因素进行了理论分析与实验研究 ,研究结果表明 :在进行反应中 ,催化剂表面积碳是造成催化剂失活的原因 ,为避免催化剂表面积碳 ,反应的最小水碳比应大于理论计算的最小水碳比。计算了在不同反应温度条件下的最小理论水碳比     

助剂对镍基生物质焦油重整催化剂性能影响的研究进展

分别以碱及碱土金属、过渡金属以及稀土金属3种常见助剂类型,探讨了不同助剂对镍基催化剂催化生物质裂解及气化重整制氢催化活性、催化剂物化特性及催化剂失活特性的影响。添加碱金属组分后,生物质热解反应速率会大幅上升,生物质焦的水蒸气气化反应得到促进,并且达到最大热解速率所需的温度也有所降低,热解产物趋向于小分子量产物;过渡金属对生物质气化过程中生成焦油的催化裂解重整具有较好的催化活性;稀土元素对甲醇水蒸气重整等催化反应有着重要的作用,镍基催化剂中加入Ce和Pr能提高甲醇转化率、改善产气组分、提高H₂的选择性。结合国内外的研究情况发现钴、镧等金属助剂有利于提升镍基催化剂重整制氢活性,催化剂积炭及表面活性颗粒的聚集是造成催化剂失活的主要原因。     

生物油催化重整制氢研究进展

随着各国新能源行业的兴起,氢能成为最具发展潜力的可再生能源。利用生物油进行催化重整是一种优良、高效的制氢方法,同时拓宽了生物油高值化利用的途径。本文对近年来该领域内的相关研究进行综述,重点介绍了原料对重整反应的影响（不同来源生物油及其模化物）、催化剂特性对重整反应的影响（负载贵金属与非贵金属）以及操作条件对重整反应的影响,对新兴的微波催化重整技术进行了简要介绍,并针对目前该领域所面临的困难提出了一些展望及发展方向,为生物油催化重整制氢提供重要理论依据。     

Steam Reforming of Bio‐Oil for Hydrogen Production: Effect of Ni‐Co Bimetallic Catalysts

Various Ni‐Co bimetallic catalysts were prepared by incorporating sol‐gel and wet impregnation methods. A laboratory‐scale fixed‐bed reactor was employed to investigate their effects on hydrogen production from steam reforming of bio‐oil. The catalyst causes the condensation reaction of bio‐oil, which generates coke and inhibits the formation of gas at temperatures of 250 °C and 350 °C. At 450 °C and above the transformation of bio‐oil is initiated and gaseous products are generated. The catalyst also can promote the generation of H₂ as well as the transformation of CO and CH₄ and plays an active role in steam reforming of bio‐oil or gaseous products from bio‐oil pyrolysis. The developed 3Ni9Co/Ce‐Zr‐O catalyst achieved maximum hydrogen yield and lowest coke formation rate and provided a better stability than a commercial Ni‐based catalyst.     

Stable Hydrogen Production from Ethanol through Steam Reforming Reaction over Nickel-Containing Smectite-Derived Catalyst

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH₄ are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H₂ reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H₂.     

Raney-Ni催化剂甘油蒸气重整制氢研究

采用管式固定床流动反应器,以Raney-Ni为催化剂,对甘油蒸气重整制氢进行了研究,考察了常压下不同温度、料液浓度和催化剂装载量对催化活性和氢气选择性的影响。结果表明:当进料浓度合适,催化剂Raney-Ni可在较低温度下呈现出对蒸气重整制氢反应较好的催化活性和选择性。当温度为280℃、料液浓度为5%(质量分数)、流量为0.5 mL/min时,碳转化率和H_2产率分别可达99.9%和93.21%,H_2和CO选择性分别为80.70%和0.20%。     

Catalyst deactivation and engineering control for steam reforming of higher hydrocarbons in a novel membrane reformer

The catalyst deactivation and reformer performance in a novel circulating fluidized bed membrane reformer (CFBMR) for steam reforming of higher hydrocarbons are investigated using mathematical models. A catalyst deactivation model is developed based on a random carbon deposition mechanism over nickel reforming catalyst. The results show that the reformer has a strong tendency for carbon formation and catalyst deactivation at low steam to carbon feed ratios for high reaction temperatures and high pressures . The trend is similar for the cases without and with hydrogen selective membranes. Based on this preliminary investigation, an engineering control approach, i.e., in-site control with a concept of critical/minimum steam to carbon feed ratio, is proposed and used to determine the carbon deposition free regions for both cases without and with hydrogen membranes. The comparison between the reported data and model simulation shows that the critical steam to carbon feed ratio predicted by the model agrees well with the reported industrial/experimental operating data.     

Catalytic steam reforming of biomass-derived tar for hydrogen production with K2CO3/NiO/γ-Al2O3 catalyst

A major problem of using Ni-based catalysts is deactivation during catalytic cracking and reforming, lowering catalytic performance of the catalysts. Modification of catalyst with alkali-loading was expected to help reduce coke formation, which is a cause of the deactivation. This paper investigated the effects of alkali-loading to aluminasupported Ni catalyst on catalytic performance in steam reforming of biomass-derived tar. Rice husk and K₂CO₃ were employed as the biomass feedstock and the alkali, respectively. The catalysts were prepared by a wet impregnation method with γ-Al₂O₃ as a support. A drop-tube fixed bed reactor was used to produce tar from biomass in a pyrolysis zone incorporated with a steam reforming zone. The result indicated that K₂CO₃/NiO/γ-Al₂O₃ is more efficient for steam reforming of tar released from rice husk than NiO/γ-Al₂O₃ in terms of carbon conversion and particularly hydrogen production. Effects of reaction temperature and steam concentration were examined. The optimum temperature was found to be approximately 1,073 K. An increase in steam concentration contributed to more tar reduction. In addition, the K₂CO₃-promoted NiO/γ-Al₂O₃ was found to have superior stability due to lower catalyst deactivation.     

Hydrocarbon steam reforming on Ni alloys at solid oxide fuel cell operating conditions

We demonstrate that supported Sn/Ni alloy catalyst is more resistant to deactivation via carbon deposition than supported monometallic Ni catalyst in steam reforming of isooctane at moderate steam to carbon ratios, irrespective of the average size of metal particles and the metal loading. The experiments were performed for average diameters of catalytic particles ranging from 30 to 500 nm and for the loading of active material ranging from 15 to 44 wt% with respect to the total mass of catalyst. The steam reforming reactions were performed at conditions that are consistent with typical solid oxide fuel cell (SOFC) operating conditions. DFT calculations show that the reasons for the enhanced carbon-tolerance of Sn/Ni compared to monometallic Ni are high propensity of Sn/Ni to oxidize carbon and lower driving force to form carbon deposits on low-coordinated metal sites.     

CH4CO2催化重整制合成气的研究进展

综述了CH₄CO₂催化重整制合成气的研究进展，分析讨论了催化剂的研究状况、反应机理、动力学、催化剂失活特性和非常规供能方式在催化重整反应中的应用等。结果表明，CO₂催化重整过程开发成功的关键是有效抑制催化剂积炭失活。     

Co/ZrO2催化乙醇水蒸汽重整制氢反应的研究

采用浸渍-热分解-氢还原法制备Co/ZrO2催化剂,并用XRD、BET比表面、TPR、差热-热重等测试分析手段对该催化剂进行表征。采用固定床反应器考察了催化剂对乙醇水蒸汽重整制氢反应的催化性能。结果表明:700℃焙烧的ZrO2以单斜和四方相形式共存,负载Co后观察不到有四方相。3%Co/ZrO2催化剂对乙醇水蒸汽重整制氢反应表现出较高的活性。在500℃、水醇比为3∶1时,乙醇的转化率达到76.6%,H2的产率和选择性为0.57mol/mol和81.8%。反应温度升高,提高了乙醇的转化率和H2产率,同时也促进了催化剂表面的积炭。     

Preparation of Hydrogen through Catalytic Steam Reforming of Bio-oil

Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor. Influential factors including temperature, weight hourly space velocity (WHSV) of bio-oil, mass ratio of steam to bio-oil (S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated. Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed, hydrogen yield and carbon selectivity were examined. The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity. Higher hydrogen selectivity and yield, and carbon selectivity were obtained at lower bio-oil WHSV. In catalytic steam reforming system a maximum steam concentration value exists, at which hydrogen selectivity and yield, and carbon selectivity keep constant. Through experiments, preferential operation conditions were obtained as follows: temperature 800~850℃, bio-oil WHSV below 3.0 h-1, and mass ratio of steam to bio-oil 10~12. The performance tests indicate that Ni-based catalysts are optional, especially Ni/a-Al2O3 effective in the steam reforming process.