生物质气化与催化剂的研究进展

生物质气化是一种在高温氧化性介质作用下将生物质热分解为可燃性气体的热解技术。为了提高生物质气化过程中气化效率、调整可燃性气体组分的含量和去除焦油,通常需要采用不同气化介质、改变气化条件或添加不同的催化剂。本文重点综述了生物质气化所使用的介质和催化剂种类以及气化条件对气化气组分,主要是H2和CO的影响规律。最后对未来生物质气化研究进行了展望,提出了几个待研究解决的问题。     

基于对生物质焦油催化裂解的催化材料

生物质能作为一种可再生能源,越来越受到广泛关注。生物质能对未来世界能源的可持续发展具有重要意义。生物质能具有多种转化途径,其中生物质气化技术能有效将其转化为高效燃气,而生物质焦油是限制生物质气化技术发展的关键所在,本文针对生物质气化过程中的核心技术焦油去除的方法做了全面总结。重点介绍了催化裂解过程中应用的4种催化剂,并对4种催化剂的组成、催化机理以及催化剂的改性优化方式以及不同裂解条件对催化效果的影响进行了分类讨论。最后展望了生物质气化技术的发展前景,提出了未来催化裂解的研究重点。     

生物质气化与催化剂的研究进展

生物质气化是一种在高温氧化性介质作用下将生物质热分解为可燃性气体的热解技术。为了提高生物质气化过程中气化效率、调整可燃性气体组分的含量和去除焦油,通常需要采用不同气化介质、改变气化条件或添加不同的催化剂。本文重点综述了生物质气化所使用的介质和催化剂种类以及气化条件对气化气组分,主要是H₂和CO的影响规律。最后对未来生物质气化研究进行了展望,提出了几个待研究解决的问题。     

高温水蒸气生物质催化气化的研究进展

在粮食加工副产物资源化利用的背景下,生物质气化技术成为生物质利用研究的重点内容。生物质气化技术的发展和应用,对推动生物质利用的节能化、环保化发展有着重要的意义。主要论述了高温水蒸气生物质催化气化的相关内容。     

国外生物质催化气化催化剂的研究进展

生物质气化技术已在国内外得到了广泛的开发和运用,但由于合成气中焦油含量较高,影响了合成气的品质,限制了生物质气化技术的应用。在生物质气化过程中应用催化剂可以有效的降低焦油的含量,调整合成气组成。对国外生物质催化气化催化剂的研究进展进行了综述,并提出了我国生物质催化气化技术的研究方向。     

生物质废弃物催化气化制取富氢燃料气

利用生物质氢可以实现 CO2 归零的排放 ,从根本上解决化石能源消耗带来的温室效应问题 ,已引起了世界各国研究者的普遍兴趣 .介绍了生物质催化气化制取富氢燃料气的研究概况 ,给出了生物质催化气化制氢的典型流程 ,讨论了在气化过程中发生的主要化学反应以及影响燃料气组成和焦油含量的一些主要影响因素 ,如气化介质的不同及催化剂的应用等     

钙钛矿催化剂在生物质热化学利用领域的研究进展

钙钛矿催化剂优异的氧化还原性能、离子迁移率、热稳定性和较低的生产成本,使得其在生物质热化学利用领域具有广阔的应用前景。基于生物质热解/气化、生物质重整制氢和生物质下游产物化学合成等应用场景,重点阐述并总结了钙钛矿催化剂的催化性能和机制。聚焦于金属阳离子的催化作用和晶格氧的氧化还原作用,从A/B位离子取代、空间结构改变等方面总结了钙钛矿催化剂的优化设计方法。为钙钛矿催化剂在生物质热化学利用领域的应用与优化指明了方向。     

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。     

高温水蒸气生物质催化气化研究进展

综述了近些年提出的高温水蒸气气化技术(HTSG),该技术不仅有利于抑制焦油生成,提高气化效率和碳的转化率,而且能够有效提高气化气中氢气含量(40%⁶0%),具有很好的研究意义和技术应用前景。此外,催化剂作为该技术的重要组成部分,通过介绍催化剂对生物质气化在产气量、气化效率、催化机理等方面的影响,重点综述其作用原理、实用性、优缺点及催化气化亟待解决的关键问题,最后给出高温水蒸气气化技术和合成类催化剂建议及其应用展望。     

高温水蒸气生物质催化气化研究进展

综述了近些年提出的高温水蒸气气化技术(HTSG),该技术不仅有利于抑制焦油生成,提高气化效率和碳的转化率,而且能够有效提高气化气中氢气含量(40%~60%),具有很好的研究意义和技术应用前景。此外,催化剂作为该技术的重要组成部分,通过介绍催化剂对生物质气化在产气量、气化效率、催化机理等方面的影响,重点综述其作用原理、实用性、优缺点及催化气化亟待解决的关键问题,最后给出高温水蒸气气化技术和合成类催化剂建议及其应用展望。     

助剂钾对镍基催化剂性能影响研究进展

镍基催化剂是生物质气化及焦油转化过程中活性最高的催化剂之一,但容易因积炭失活影响寿命,降低制氢过程的经济性。添加助剂不仅可以有效提高催化剂的抗积炭能力,还可以提高催化剂的稳定性。本文综述了助剂钾对镍基催化剂抗积炭能力及反应活性的影响,分析了助剂钾影响积炭生成和积炭气化的机理。助剂钾能够提高镍基催化剂的抗积炭能力,抑制催化剂的烧结,提高催化剂的稳定性。未来的研究方向是进一步考察助剂钾的种类、添加方式对镍基催化剂的抗积炭能力及焦油转化活性的影响与本质原因,以制备出具有高活性、高抗积炭能力、长寿命的生物质气化镍基催化剂。     

生物质气化制富氢合成气的研究进展

生物质气化制取富氢合成气因其原料的清洁可再生性、产物应用方式的多样性被认为是最具发展前景的制氢方式之一。催化剂对调控生物质气化产物组成及焦油的裂解具有重要作用。本文综述了化石能源制氢、水分解制氢和生物质制氢方法,分析了生物质气化制氢的优势和局限性,以及存在的问题;重点介绍了生物质气化制氢的影响因素(气化剂、反应温度和催化剂)和用于生物质气化的主要催化剂种类(镍基、白云石和碱及碱土金属催化剂)及其特点,分析国内外生物质气化制取富氢合成气和催化剂的研究现状,探讨了催化气化制取富氢合成气的发展前景,提出有待解决的问题和研究方向。     

生物质炭化热解气催化重整制取费-托合成气研究进展

生物质热解气是一种高热值的可燃气体,具有重要的开发利用价值,但由于其复杂的组分,多焦油和CO₂、CH₄等成分对热解气化过程以及相关的设备都有较大的危害,而冷凝下来形成的黏稠液体易造成管道堵塞,直接燃用产生的炭黑会造成环境污染,成为制约热解气进一步开发利用的主要因素。本文分析了热解气催化重整制取费-托合成气的可行性,分别介绍了连续和分段式热解-催化重整设备,镍基、钙基、铁基、碱金属类、生物炭等催化剂,以及热解气分离提纯技术等方面的研究现状,分析了目前热解气制取费-托合成气研究中存在的催化重整设备规格不统一、缺乏相关的行业标准、不同催化剂与催化剂助剂的催化重整效果、机理尚不明确等问题,并提出了采用分段式热解-催化重整设备,并以炭化产品生物炭作为催化重整催化剂的未来研究方向,开辟了生物质炭化热解气开发利用的新途径。     

Development of new nickel based catalyst for tar reforming with superior resistance to sulfur poisoning and coking in biomass gasification

Gasification of tar by catalytic steam reforming was examined in the gasification process of biomass, such as dried sewage sludge and wood chips. The tar reforming characteristics of the newly-developed Ni/MgO–CaO (based on dolomite) catalyst which was doped with WO₃ as a sulfur-resistant promoter, was investigated using a simulated gas containing naphthalene as tar. The result has confirmed that the developed catalyst shows a high naphthalene reforming activity and is stable even in gas containing hydrogen sulfide. The catalyst also exhibited superior resistance to coking as well as sulfur poisoning compared to several commercial steam-reforming catalysts.     

生物质气化技术及焦油裂解催化剂的研究进展

本文综述了国内外研究机构在生物质气化技术方面的研究进展,主要是对不同于传统气化炉结构的优化设计和对焦油催化裂解所用的催化剂的研究进行了评述,最后指出了进一步的研究与发展方向:如生物质气化反应器的模拟;焦油催化裂解反应机理的研究和动力学模型的建立。     

Deactivation of catalysts for fossil coal and biomass conversion

Increasing interest in the use of resources of organic raw materials alternative to petroleum stimulates researchers to study the catalytic intensification of fossil coal and vegetable biomass conversion. The industrial use of the developed technologies is restricted by the problem of enhanced catalyst deactivation. The main reasons for catalyst deactivation in solid organic raw materials conversion are considered in the review. The possible ways of the successful solution of the problem of catalyst deactivation in the processes of coal and biomass liquefaction and gasification and wood delignification and hydrolysis are exemplified by the studies accomplished over the last decade. In the case of technologies using the synthetic catalysts, the methods of their regeneration developed for the catalytic processing of heavy petroleum residues can be applied. The catalyst regeneration is not demanded for the processes accomplished in a fluidized catalytic bed under the conditions of catalyst loss as a result of its attrition and in the case of the application of melted catalysts, cheap iron-containing catalysts, catalytically active slag materials, and natural minerals. The substitution of dissolved catalytic systems for solid catalysts allows for the diminishing of their deactivation in the processes of wood delignification and hydrolysis.     

Bench- and Pilot-Scale Studies of Reaction and Regeneration of Ni–Mg–K/Al2O3 for Catalytic Conditioning of Biomass-Derived Syngas

The National Renewable Energy Laboratory (NREL) is collaborating with both industrial and academic partners to develop technologies to help enable commercialization of biofuels produced from lignocellulosic biomass feedstocks. The focus of this paper is to report how various operating processes, utilized in-house and by collaborators, influence the catalytic activity during conditioning of biomass-derived syngas. Efficient cleaning and conditioning of biomass-derived syngas for use in fuel synthesis continues to be a significant technical barrier to commercialization. Multifunctional, fluidizable catalysts are being developed to reform undesired tars and light hydrocarbons, especially methane, to additional syngas, which can improve utilization of biomass carbon. This approach also eliminates both the need for downstream methane reforming and the production of an aqueous waste stream from tar scrubbing. This work was conducted with NiMgK/Al₂O₃ catalysts. These catalysts were assessed for methane reforming performance in (i) fixed-bed, bench-scale tests with model syngas simulating that produced by oak gasification, and in pilot-scale, (ii) fluidized tests with actual oak-derived syngas, and (iii) recirculating/regenerating tests using model syngas. Bench-scale tests showed that the catalyst could be completely regenerated over several reforming reaction cycles. Pilot-scale tests using raw syngas showed that the catalyst lost activity from cycle to cycle when it was regenerated, though it was shown that bench-scale regeneration by steam oxidation and H₂ reduction did not cause this deactivation. Characterization by TPR indicates that the loss of a low temperature nickel oxide reduction feature is related to the catalyst deactivation, which is ascribed to nickel being incorporated into a spinel nickel aluminate that is not reduced with the given activation protocol. Results for 100?h time-on-stream using a recirculating/regenerating reactor suggest that this type of process could be employed to keep a high level of steady-state reforming activity, without permanent deactivation of the catalyst. Additionally, the differences in catalyst performance using a simulated and real, biomass-derived syngas stream indicate that there are components present in the real stream that are not adequately modeled in the syngas stream. Heavy tars and polycyclic aromatics are known to be present in real syngas, and the use of benzene and naphthalene as surrogates may be insufficient. In addition, some inorganics found in biomass, which become concentrated in the ash following biomass gasification, may be transported to the reforming reactor where they can interact with catalysts. Therefore, in order to gain more representative results for how a catalyst would perform on an industrially-relevant scale, with real contaminants, appropriate small-scale biomass solids feeders or slip-streams of real process gas should be employed.     

生物质热化学法制氢技术的研究进展

介绍木质生物质热化学法生产氢气的四条主要技术路线,分别是生物质气化制氢、生物质热解油制氢、生物质超临界水气化制氢、源于生物质的小分子有机物催化重整制氢方法,着重从化学反应机理、热力学模拟、催化剂种类、工艺开发、工业化进展等方面总结生物质热化学制氢技术的最新研究进展,分析了各类小分子制氢的热力学规律,并指出工业化过程存在...