联合CO2捕集的生物质化学链气化制备合成气系统分析

本文提出以Fe₂O₃为载氧体、以CaO捕集CO₂的生物质化学链气化系统,利用Aspen Plus软件对该系统进行了模拟,以合成气组成（干基）、合成气氢碳比、含碳产物的碳摩尔分布、冷气效率及收率等为系统性能评价指标,重点分析了燃料反应器温度（T_FR）、载氧体Fe₂O₃与生物质碳摩尔比（Fe₂O₃/C）、水蒸气与生物质碳摩尔比（Steam/C）、CaO与生物质碳摩尔比（CaO/C）等系统参数对固体生物质化学链气化系统的影响。结果表明,在T_FR = 825℃、Fe₂O₃/C = 0.5、Steam/C = 0.71和CaO/C = 0.26条件下,合成气制备系统性能较优,合成气中H₂和CO₂含量分别为55.2%和15.4%,氢碳比为1.93,冷气效率为78.2%,被CaCO₃捕集的生物质碳为18.2%,收率（湿气基）为1.95 Nm³/kg_biomass,其中合成气中H₂和CO收率为1.24 Nm³/kg_biomass。     

定向调控生物质CO_(2)/H_(2)O气化制取H_(2)/CO合成气的热力学分析北大核心CSCD

文章对以CO_(2)/H_(2)O为气化剂的生物质气化,生产H_(2)/CO为3∶1的合成气的反应过程进行了热力学分析。研究发现,提高气化温度可以增大H_(2)和CO的总产率,且超过700℃基本没有CH_(4)和C的生成;通过控制气化剂CO_(2)/H_(2)O的通入比例,可以实现H_(2)/CO合成气的定向调控;CO_(2)通入量的增大可以提高CO产率,降低H_(2)/CO为3∶1的合成气的气化温度(临界温度)和所对应的(H_(2)+CO)总产量;H_(2)O通入量的增加可以增大H_(2)产率,提高临界温度和所对应的(H_(2)+CO)总产量。文章拟合出临界温度和所对应的(H_(2)+CO)总产量与CO_(2)和H_(2)O通入量的关系式,为工业生产H_(2)/CO为3∶1的合成气以及后续甲烷化提供理论支持。     

梨木炭蒸汽气化制取富氢燃气的试验研究

生物质气化技术已得到广泛的应用,但气化过程产生的焦油会影响设备稳定运行。为了大幅减少焦油的干扰,以梨木的热解炭为原料,在管式炉中进行水蒸气气化制取富氢燃气试验研究,探究了反应温度、K₂CO₃添加量及利用次数对气化特性的影响。结果表明：900℃时H₂的产气量为2.19 L/g,合成气中H₂含量超过58%;K₂CO₃添加量为10%时产气效果最佳,此时合成气中H₂+CO含量达到了88.5%。当K₂CO₃催化剂在第三次利用时,仍有较好的催化效果。     

CuFe2O4氧载体与小麦秆-煤化学链共气化研究

以小麦秆与印尼褐煤为原料,制备具有尖晶石结构的CuFe₂O₄复合氧载体,在自制多功能反应器上,系统研究了CuFe₂O₄氧载体反应活性及小麦秆和印尼褐煤化学链共气化特性,重点关注小麦秆和煤不同掺混比、气化温度、氧载体过量系数和水蒸气输入量这4个关键运行参数的影响。结果表明：CuFe₂O₄复合氧载体中Cu-Fe的协同作用有助于晶格氧的有效传递和反应活性的提升,而小麦秆和印尼褐煤化学链共气化时碳转化率及冷煤气效率比单一燃料的大,促进了高品质合成气的形成;小麦秆和褐煤在与CuFe₂O₄化学链气化过程中的最优运行参数为共气化温度950℃、氧载体过量系数0.2、水蒸气通入体积流量0.125 mL/min、小麦秆-印尼褐煤掺混质量比1∶1,在此最优条件下,合成气产量高达1.262 m³/kg, H₂与CO体积比为1.69,碳转化率为89.7%,合成气选择性为63.2%。     

CO2气氛下危废污泥与煤、废活性炭的共气化特性

采用热重分析法对CO₂气氛下工业危废污泥与煤和废活性炭在不同比例下混合进行共气化的失重过程、气化反应动力学和协同气化效应进行了研究．随着混合燃料中煤/废活性炭比例的提高，混合燃料的失重率和最大失重速率都相应大幅提高．随气化温度升高，相比污泥单独气化，混合燃料的协同气化反应得以加强．60%污泥混合40%煤/活性炭时表现出更高的协同性指数，焦炭气化阶段的反应活化能为污泥单独气化时的24%～31%．与煤相比，废活性炭与污泥的协同气化效应更为显著．在此基础上利用管式气化实验炉对混合燃料的产气特性进行了初步研究．产气主要有效成分中CO体积占比最大，其次为H₂和CH₄．污泥单独气化时，产气中CO含量随CO₂流量增加逐渐降低；与煤或废活性炭共气化时，CO含量则随CO₂流量增大而逐渐增加．随煤和废活性炭混合比提高，H₂、CH₄含量逐渐上升，CO则相应降低．CO的含量整体受混合比和CO₂流量共同影响．     

水蒸气气氛下生物质与聚丙烯共气化产气特性数值分析

搭建生物质与废塑料共气化动力学模型,并用实验数据对其进行验证。选用6种生物质和聚丙烯作为共气化反应物,以水蒸气为气化剂,计算气化温度在300～1000℃之间、气化压强在0.1～0.8 MPa之间、聚丙烯和松木锯末质量比例在0.5～2.5之间,以及不同生物质类型等对生物质和聚丙烯共气化产气特性的影响。结果表明：松木锯末气化中添加聚丙烯后,最高产气量和最大产气速率增加,最高产气总流量提高21.46%,最高产气速率提高4.64%,H₂和CO最高产量分别提高54.27%和79.51%;压强增加不利于提高共气化产气的H₂和CO含量,有利于提高CH₄含量;6种常见生物质和聚丙烯共气化产氢量大小顺序为：果皮>棉花秆≈玉米秸秆>杨树木屑>稻秆>条浒苔;聚丙烯掺混比率增加有利于提高H₂、CO和CH₄等组分产量。     

钙钛矿型LaFeO_(3)载氧体生物质化学链气化热力学分析及实验研究北大核心CSCD

文章针对基于LaFeO_(3)载氧体的木屑生物质化学链气化特性,开展了热力学过程模拟与分析,并搭建了固定床实验装置,研究了载氧体添加量(O/B)、气化温度和水蒸气量对合成气品质的影响。热力学分析结果表明:相比传统Fe_(2)O_(3)载氧体,LaFeO_(3)不易与合成气进一步反应,更适合生物质的化学链气化过程,且气化温度升高有利于提升合成气产率,增大LaFeO_(3)添加量也会促进合成气生成,而过多的Fe_(2)O_(3)则会进一步氧化合成气导致产气率下降;添加水蒸气可明显提高合成气中H2占比。实验结果表明,提高反应温度和载氧体添加量能够提高合成气品质,但过量水蒸气反而不利于合成气的转化。在O/B为0.6、气化温度为900℃、水蒸气流量为0.3mL/min的最佳工况下,基于LaFeO_(3)的木屑化学链气化过程的转化效率达到97.09%。研究成果可为生物质固废的能源化利用与推广提供科学依据。     

玉米秸秆循环流化床热解气化试验

采用循环流化床气化中试装置对玉米秸秆进行了气化试验,分别在常温空气与250℃预热空气条件下,研究了空气当量比（ER）和原料含水率对气化特性的影响规律。结果表明：随着ER的增大,循环流化床气化炉内的反应温度升高,气化燃气中的CO₂含量增加,焦油与CO含量及燃气热值降低,气化效率随ER的增大呈先增大后减小的趋势;随着气化原料含水率的增加,循环流化床气化炉内的平均温度下降,燃气中的CO₂与H₂及焦油含量逐渐升高,CO含量下降,CH₄与C_nH_m含量均为先增加后减少。与常温空气工况相比,预热空气工况下的燃气热值与气化效率均有一定程度的提高。采用预热空气为气化介质,提高气化剂温度,可显著促进玉米秸秆的气化反应,提升气化效率。     

下吸式固定床的生物质H2O/CO2气化数值模拟研究

利用Aspen Plus 软件建立干桦木屑在下吸式固定床气化炉中的气化模型,模拟值与文献实验值吻合良好。利用Aspen Plus的灵敏度分析模块模拟分别以水蒸气（H₂O）和二氧化碳（CO₂）为气化剂时气化剂/生物质碳比（GC值）对气化结果的影响,并结合H₂O、CO₂各自的特点研究其复合气化。结果表明,H₂O气化时可获得富氢煤气,但其净CO₂排放量较高;CO₂气化时碳转化率及冷煤气效率较低,但净CO₂排放量较低;H₂O、CO₂复合气化使碳转化率及冷煤气效率略有降低,但可有效减少气化系统中的净CO₂排放量。     

生物质气流床气化制取合成气的试验研究

利用一套小型生物质层流气流床气化系统,研究了稻壳、红松、水曲柳和樟木松4种生物质在不同反应温度、氧气/生物质比率(O/B)、水蒸汽/生物质比率(S/B)以及停留时间下对合成气成分、碳转化率、H2/CO以及CO/CO2比率的影响.研究表明4种生物质在常压气流床气化生成合成气最佳O/B范围为0.2～0.3(气化温度.1300℃),高温气化时合成气中CH4含量很低,停留时间为1.6s时其气化反应基本完毕.加大水蒸汽含量可增加H2/CO比率,在S/B为0.8时H2/CO比率都在1以上,但水蒸汽的过多引入会影响煤气产率.气化温度是生物质气流床气化最重要的影响因素之一.     

Thermo-neutral production of metals and hydrogen or methanol by the combined reduction of the oxides of zinc or iron with partial oxidation of hydrocarbons

Stoichiometry and temperature requirements are determined for combining the endothermic reduction of metal oxides (ZnO, Fe₂O₃, and MgO) with the exothermic partial oxidation of hydrocarbons (CH₄, n-butane, n-octane, and n-dodecane) in order to co-produce simultaneously metals and syngas in thermo-neutral reactions. Thermogravimetric and GC measurements on the combined reduction of ZnO and Fe₂O₃ with the partial oxidation of CH₄ were conducted at 1400 K to experimentally verify the products predicted by equilibrium computations, and resulted in the complete reduction to Zn and Fe, respectively, while producing high quality syngas. A preliminary economic assessment that assumes a natural gas price of 11.9 US$/MWh and credit for zinc sale at 750 US$/metric ton, indicates a competitive cost of hydrogen production at 6.0 US$/MWh, based on its high heating value. The proposed combined process offers the possibility of co-producing metals and syngas in autothermal non-catalytic reactors, with significant avoidance of CO₂ emission.     

Ni-Co双金属催化剂上沼气重整制氢宏观动力学

用传统湿式浸渍法制备La2O3掺杂的商业γ-Al2O3负载的沼气重整催化剂Ni-Co/La2O3-γ-Al2O3,通过对NiCo双金属催化剂上沼气重整制氢在常压下的宏观动力学分析,得出该催化剂上CH4与CO2消耗、H2与CO生成时的表观反应速率方程.通过改变进料中CH4与CO2的分压,求出各物质的反应分级数,确定总反应...     

下吸式固定床的生物质O2/CO2分段气化流程模拟

建立干桦木屑在下吸式固定床气化炉中的Aspen Plus气化模型,该模型预测煤气组成和煤气热值,与文献试验结果吻合良好。利用灵敏度分析模块模拟了氧碳比、CO₂/C对气化结果的影响,并提出O₂/CO₂分段气化流程,对比常规的CO₂气化特征,分析了CO₂/C对气化结果的影响。结果表明,纯氧气化时可获得高H₂和CO浓度的气化气,但其净CO₂排放量较高,氧碳比增加使碳转化率逐渐增加、冷煤气效率先增加后降低;CO₂作为气化剂时,随着CO₂/C的增加,净CO₂排放量逐渐减少,但碳转化率及冷煤气效率大幅降低;与常规CO₂气化相比,O₂/CO₂分段气化在保持低CO₂排放量的同时,可有效增加气化过程中的碳转化率及冷煤气效率。     

Effect of Bi2O3 content on characteristics of Bi2O3–GDC systems for direct methane oxidation

Ceramic systems of Bi₂O₃ and gadolinia-doped ceria (GDC) solid mixture were prepared as catalysts for direct methane oxidation. These systems were characterized by temperature-programmed reduction using hydrogen and carbon monoxide, temperature-programmed reaction of methane, fixed-temperature direct methane oxidation, and X-ray diffraction analysis. Adding Bi₂O₃ to GDC promotes both hydrogen and CO oxidation activities, because of the presence of surface Bi₂O₃ and the high content of mobile oxygen in Bi₂O₃. The reactivity of CO with surface lattice oxygen is enhanced to a higher extent than that of H₂, and this enhanced extent shows a maximum in Bi₂O₃ content. Such a maximum also exists for the catalytic activity of direct methane oxidation. A synergistic effect occurs due to a combination of the high methane reactivity of GDC and the high content of mobile oxygen in Bi₂O₃. The CO₂ selectivity of direct methane oxidation can be modulated by varying the Bi₂O₃ content. The mixing of Bi₂O₃ with GDC also increases the self-de-coking capability of the catalyst during direct methane oxidation, which stabilizes the activity.     

Thermodynamic possibilities and constraints for pure hydrogen production by iron based chemical looping process at lower temperatures

Iron offers the possibility of transformation of a syngas or gaseous hydrocarbons into hydrogen by a cycling process of iron oxide reduction (e.g. by hydrocarbons) and release of hydrogen by steam oxidation. From the thermodynamic and chemical equilibrium point of view, the reduction of magnetite by hydrogen, CO, CH₄ and a model syngas (mixtures CO + H₂ or H₂ + CO + CO₂) and oxidation of iron by steam has been studied. Attention was concentrated not only on convenient conditions for reduction of Fe₃O₄ to iron at temperatures 400–800 K but also on the possible formation of undesired soot, Fe₃C and iron carbonate as precursors for carbon monoxide and carbon dioxide formation in the steam oxidation step. Reduction of magnetite at low temperatures requires a relatively high H₂/H₂O ratio, increasing with decreasing temperature. Reduction of iron oxide by CO is complicated by soot and Fe₃C formation. At lower temperatures and higher CO₂ concentrations in the reducing gas, the possibility of FeCO₃ formation must be taken into account. The purity of the hydrogen produced depends on the amount of soot, Fe₃C and FeCO₃ in the iron after the reduction step. Magnetite reduction is the more difficult stage in the looping process. Pressurized conditions during the reduction step will enhance formation of soot and carbon containing iron compounds.     

Promising alloys for intermediate-temperature solid oxide fuel cell interconnect application

The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn₂O₃/TiO₂ surface layer and/or a (Mn, Cr)₃O₄ spinel outer layer atop a Cr₂O₃ inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr₂O₃ inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys.     

Pilot scale autothermal gasification of coconut shell with CO2-O2 mixture

This paper explored the feasibility and benefit of CO₂ utilization as gasifying agent in the autothermal gasification process. The effects of CO₂ injection on reaction temperature and producer gas composition were examined in a pilot scale downdraft gasifier by varying the CO₂/C ratio from 0.6 to 1.6. O₂ was injected at an equivalence ratio of approximately 0.33–0.38 for supplying heat through partial combustion. The results were also compared with those of air gasification. In general, the increase in CO₂ injection resulted in the shift of combustion zone to the downstream of the gasifier. However, compared with that of air gasification, the long and distributed high temperature zones were obtained in CO₂-O₂ gasification with a CO₂/C ratio of 0.6–1.2. The progress of the expected CO₂ to CO conversion can be implied from the relatively insignificant decrease in CO fraction as the CO₂/C ratio increased. The producer gas heating value of CO₂-O₂ gasification was consistently higher than that of air gasification. These results show the potential of CO₂-O₂ gasification for producing high quality producer gas in an efficient manner, and the necessity for more work to deeply imply the observation.     

熔融盐对高含氮废弃物气流床气化产气调质与污染物脱除特性研究

在生物质气流床（5 kg/h）气化和熔融盐调质净化装置上,进行了熔融盐对高含氮废弃物气流床气化产气的调质与污染物脱除实验,考察了不同熔融盐温度、不同静液高度对出口气体调质和含N、S、Cl污染物脱除特性的影响。结果表明：经过熔融盐调质后,产气中CO与CO2浓度下降,H2浓度明显上升。当温度从380℃升高至580℃时,H2/CO值提高至7.3。随着静液高度的提高,出口气体中CO2与CO浓度下降,H2浓度由30.1%提高至36.8%;熔融盐对高含氮废弃物气流床气化产气中含N、S、Cl污染物有较明显的脱除效果,H2S、SO2、HCl与含氮污染物中的HCN与NOx已完全脱除,当温度为580℃、静液高度为67.5 mm时,NH3脱除率达到96%。