生物质燃气催化重整净化的特性研究

通过改变生物质燃气重整过程中重整温度、反应时间、水蒸气的添加等参数,考察了国产烃类蒸汽转化催化剂Z405重整净化生物质燃气的性能及对合成气化学当量比的调变作用。结果表明:在Z405的作用下,生物质燃气中CH4和C2转化率均高达95%以上,合成气中CH4和C2的含量分别低于0.500%和0.005%,H2与CO含量有显著增加,CO2含量有所减少。添加水蒸气后H2/CO值较之无水蒸气的添加发生了显著变化,从0.70提高到1.15,气体低热值有所增大。提高重整温度对生物质合成气组分具有显著的调变作用,H2和CO含量增幅随温度升高而增加,CH4与C2组分含量降低幅度也随温度升高而增加。但当重整温度超过780℃时,对合成气组分调整作用不明显。重整生物质燃气组分在60min内无明显改变,未检测到催化剂活性降低、失重及积炭。     

木屑炭水蒸气催化气化制取合成气研究

以木屑炭为原料,K2CO3作为催化剂,以固定床气化炉为实验设备,进行水蒸气催化气化木屑炭的探究。考察木屑炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H2/CO比值随K2CO3催化剂质量分数(0~8%)、水蒸气流量(0.15~0.35 g/(min·g))、气化温度(800~950℃)变化的规律。实验结果表明:K2CO3催化剂可显著提升碳转化率及产氢率,K2CO3质量分数为8%时,碳转化率和产氢率分别达到86.3%和125.6 g/kg,同时合成气中CO体积分数显著增加,H2/CO比值降至2.43。增加水蒸气流量,合成气中H2含量显著增大,H2/CO比值随之增大。温度可有效促进炭气化过程,950℃时碳转化率和产氢率分别达到84.3%和127.1 g/kg,但合成气中CO体积分数增大,H2/CO比值降至2.48。实验得到H2/CO比值在2.43~5.16范围的合成气。气化反应温度在900℃、水蒸气0.2 g/(min·g)、K2CO3质量分数3%时,碳转化率可达80.4%,产氢率109.6 g/kg,合成气中(H2+CO)体积分数82.4%,同时H2/CO比值高达3.05。     

铂基催化剂快速部分催化氧化甲烷的研究

以Al 2O 3为载体,采用浸渍法制备Pt/Al 2O 3催化剂,通过测量重整反应过程中催化剂的温度分布情况,研究了改变甲烷快速部分氧化重整反应中反应条件(反应气体预混合温度、N 2体积比例、CH 4/O 2比)对反应物的转化率及产物选择性的影响。研究发现,催化剂床层温度的上升可以促进CH 4的转化,使H 2和CO的选择性升高且H 2与CO的物质的量的比(简称H 2/CO比,依此类推)升高。N 2体积比例及CH 4/O 2比的升高,会降低催化剂床层温度,进一步造成CH 4的转化率和H 2/CO比降低,但与仅降低混合气预热温度不同的是,提高N 2体积比例及CH 4/O 2比会造成H 2和CO的选择性升高,这可能是催化剂表面的活性氧导致的。通过对甲烷在Pt催化剂上的反应机理进行了初步讨论,认为甲烷的快速部分催化氧化反应为多种反应路径共存,不同的反应条件下各种反应路径所占比例会发生变化。     

木屑高温水蒸气气化制备合成气研究

在常压固定床反应器中进行木屑高温水蒸气气化制取合成气研究。分别在750~1000℃温度和0.32~1.02g/min水蒸气流量下进行实验,反应时间为10 min。主要研究反应温度和水蒸气流量对碳转化率、合成气产率及合成气组分的影响。研究结果表明,木屑水蒸气气化具有很高的反应活性,合成气产率在0.81~1.74 L/g之间;反应温度和水蒸气流量对碳转化率和合成气热值及组分影响显著;在反应温度950℃,水蒸气流量0.67 g/min时,碳转化率达到最高值99.47%;合成气主要由H2、CO、CO2、CH4及少量CnHm组成,其中(H2+CO)比例达到63%~75%,合成气热值在10.5~11.5 MJ/m3之间,H2/CO比在1.0~2.3之间。     

生物质气一步法合成二甲醚化学平衡分析

对生物质基合成气合成二甲醚反应体系进行热力学参数计算.选取CO、CO2加氢合成甲醇及甲醇脱水生成二甲醚为独立反应,CO、CO2、二甲醚为关键组分,提出了合成气合成二甲醚的计算模型.讨论了温度、压力对生物质气合成二甲醚化学平衡的影响.结果表明:CO平衡转化率、DME平衡收率随温度的升高而下降;随压力升高,CO平衡转化率、DME平衡收率增加.     

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.     

生物质蒸汽气化模拟研究

利用化学热力学软件(GasEQ)模拟了生物质蒸汽气化过程中温度、水蒸气与物料质量比(S/M)以及CO2浓度对H2,CH4和CO的影响;研究了冷合成气低位热值(LHV)和气化能量转化效率(q)随各参数变化的规律,并且考虑了外部能量的消耗。模拟研究得到:随着温度的升高,合成气的LHV总体表现出降低,并且q先增加后微弱下降,认为存在一个最优的气化温度(800⁹00℃);高S/M有利于H2的生成,提高H2的体积浓度,但水蒸气的增加,降低了LHV值,并且q先增加后减少,因为水蒸气会消耗大量外部能量,存在一个最经济的气化S/M;随着反应气中CO2浓度的升高,促进了生物质气化,并使CO浓度升高和H2浓度降低。     

小麦秸秆真空氧载体气化特性实验研究

在自制的生物质真空氧载体气化反应装置上,考察无氧载体时反应温度对气体产物分布及合成气中H_2和CO总含量的影响情况,研究氧载体对小麦秸秆真空气化过程的影响规律,并借助扫描电镜(SEM)对反应前后的氧载体进行表征。实验结果表明:无氧载体时,随着反应温度的升高,合成气中H_2和CO含量均逐渐增大,750℃时H_2含量达到10.13%;当反应温度从550℃升高到800℃时,反应温度对CO_2含量影响最为显著,CO_2含量从27.31%减小到14.43%。有氧载体时,在上述反应温度范围内,H_2含量从6.43%升至13.62%,合成气中H_2/CO值、H_2和CO总含量均随反应温度的升高而增大;氧载体可增大气体产物中H_2与CO产量,同时H_2/CO值也明显增大,说明氧载体可促进生物质气化反应;在真空条件下,氧载体并未发生明显烧结,且反应后的氧载体结构更有利于生物质气化,但其机械强度有所降低。     

基于铁矿石载氧体加压煤化学链燃烧的试验研究

在反应温度为970℃、压力范围为0.1～0.6 MPa的条件下,以铁矿石为载氧体,采用固定床反应器,对煤化学链燃烧进行了试验研究,考察了加压对燃料反应器内水蒸气气氛下煤化学链燃烧的反应特性.结果表明:加压能加快煤水蒸气气化速率,加强水气转换反应,并对煤气组分产生影响,使CO浓度降低,CO2和H2浓度升高;加压后还原反应烟气中不再含有H2,CO和CH4的浓度也变得很低,说明加压可提高还原反应中煤气的转化率;随着压力的升高,碳转化率先升高后又降低,存在着一个中间压力值,使碳转化率最高.     

旋转滑动弧促进甲烷干重整制取合成气

实验考察了常温常压下,利用旋转滑动弧等离子体促进CH4-CO2重整制取合成气的效果,分析了放电电压、CH4体积分数和供气流量等参数对反应物转化率、产物选择性和经济效益等的影响.实验发现,CH4体积分数增加,会使CH4转化率升高,CO2转化率先增后减.流量增加,会使CH4、CO2转化率整体呈下降趋势.流量为12,L/min时,CH4、CO2最高转化率分别为43.78%、42.66%,H2、CO最高选择性分别为44.20%、32.48%,H2/CO体积比范围为0~1.56.单位摩尔量合成气所需电耗最低为195.06,kJ/mol,能量转化效率最高为46.535%.     

炭体系下二氧化碳重整甲烷三维数值模拟

炭催化CO2重整CH4.制合成气是实现煤炭资源的多联产和洁净化利两相流第二相体积份额大小影响的欧拉双流体模型的基础上,结合多个异相催化反应动力学模型,建立了包含传热、传质、化学反应在内的炭体系下二氧化碳重整甲烷反应器三维数学模型.利用该模型对 12 mm实验室反应器进行了三维数值模拟,得到了重整反应器内气体浓度分布、速度分布、以及产物中H2/CO摩尔比等重要参数.数值模拟结果与试验结果基本吻合.对指导重整反应器的放大和工业应用具有指导意义.     

Reforming of methane and carbon dioxide by DC water plasma at atmospheric pressure

An experimental plasma chemical reactor, equipped with a novel water plasma torch, was used for reforming methane and carbon dioxide mixture to produce synthesis gas (syngas). Water plasma is generated by the torch at atmospheric pressure, in the absence of carrier gases, water cooling system and special steam supply system. The influence of the ratio of CO₂ to CH₄ and total feed gas rate on syngas production, composition and energy conversion efficiency were investigated. Compared to other plasma technologies, the higher reaction performance was obtained by the novel water plasma process. The results show that, under optimum experimental conditions, the energy conversion efficiency reaches up to maximum value of 1.87 mmol/kJ and the highest energy efficiency of 74.63% is achieved, which is higher than that of other plasma processes. Furthermore, the obtained syngas with high mole ratio of H₂ to CO (close to 2) is suitable for the direct industrial application.     

A multi-objective optimization of three conflicting criteria in a methane tri-reforming reactor

For the first time, a multi-objective optimization approach is used to optimize energy efficiency with other conflicting objectives for tri-reforming of methane. A 2-D axisymmetric model over nickel based catalysts is established to maximize the energy efficiency, syngas production and CO₂ conversion. The inlet temperature, oxygen/methane and carbon dioxide/methane are considered as the decision variables. The attained results revealed that at the utopia point for maximization of H₂/CO ratio and energy efficiency, not only H₂/CO ratio and energy efficiency reach 2.76 and 42.21, but also CH₄ consumption overtakes 60%. Besides, when we consider maximization of CO₂ conversion and energy efficiency as the objectives, 1% compromise in the best value of energy efficiency results in an increment of 40% in the value of CO₂ conversion. Finally, the third optimization reveals that the CH₄ conversion is above 80% and the final mole fraction of H₂ is approximately 0.15.     

整体型催化剂上甲烷自热氧化制合成气

用镍金属制备了一整体催化剂并与负载铑和铂比较了甲烷氧化制合成气的性能。结果表明，镍金属催化剂上甲烷转化率、H2和CO的选择性与铑催化剂相当，而且稳定性非常好。反应中加入H2O和CO2的实验表明，产物中H2／CO的比例可以直接调节。     

Reduction time effect on structure and performance of Ni–Co/MgO catalyst for carbon dioxide reforming of methane

Reducing catalysts with hydrogen is an important process for carbon dioxide reforming methane since metallic active sites are exposed and dispersed during the reduction process. In this work, Ni–Co/MgO catalysts were prepared for syngas production by using a multiple-impregnation method with a carbon dioxide reforming methane reaction. Activity evaluation showed that catalysts that reduced for 1 h exhibited superior catalytic activity with methane and carbon dioxide conversion at 92% and 97%, respectively, and the syngas ratio close to unity (0.98). The high activity is ascribed to the better metal dispersion (10.5%) and smaller active metal particle size (10 nm). Raman spectra analysis indicated that catalysts that reduced for a longer time possessed larger active metal particle size, and were more susceptible to the formation of graphite-like carbon deposits, which were difficult to be removed by the active oxygen species derived from carbon dioxide dissociation.     

Enhancement of the quality of syngas from catalytic steam gasification of biomass by the addition of methane/model biogas

In this study, methane and model biogas were added during the catalytic steam gasification of pine to regulate the syngas composition and improve the quality of syngas. The effects of Ni/γ-Al₂O₃ catalyst, steam and methane/model biogas on H₂/CO ratio, syngas yield, carbon conversion rate and tar yield were explored. The results indicated that the addition of methane/model biogas during biomass steam gasification could increase the H₂/CO ratio to about 2. Methane/model biogas, steam and Ni/γ-Al₂O₃ catalyst significantly affected the quality of syngas. High H₂ content syngas with H₂/CO ratio of about 2, biomass carbon conversion >85% and low tar yield was achieved under the optimum condition: S/C = 1.5, α = 0.2 and using Ni/γ-Al₂O₃ catalyst. According to ANOVA, methane and catalyst were the key influencing factors of the H₂/CO ratio and syngas yield, and the tar yield mainly depended on the Ni/γ-Al₂O₃ catalyst. Biogas, as a more environmentally friendly material than methane, can also regulate the composition of syngas co-feeding with biomass.     

H2-rich syngas production from biogas reforming: Overcoming coking and sintering using bimetallic Ni-based catalysts

Dry reforming of methane is a very appealing catalytic route biogas (mainly composed by greenhouse gases: carbon dioxide and methane) conversion into added value syngas, which could be further upgraded to produce liquid fuels and added value chemicals. However, the major culprits of this reaction are coking and active phase sintering that result in catalysts deactivation. Herein we have developed a highly stable bimetallic Ni–Rh catalyst supported on mixed CeO₂–Al₂O₃ oxide using low-noble metal loadings. The addition of small amounts of rhodium to nickel catalysts prevents coke formation and improves sintering resistance, achieving high conversions over extended reaction times hence resulting in promising catalysts for biogas upgrading.     

基于铁矿石载氧体的生物质化学链气化机理研究

在单批次进料小型流化床上,以稻壳为生物质燃料,研究了床料、气化温度、水蒸气体积分数以及载氧体载氧量与生物质含碳量的摩尔比(O/C)对生物质化学链气化反应特性的影响,并考察了铁矿石的长期交替氧化还原过程中的反应特性,分析了在小型流化床,水蒸气气氛气化条件下,铁矿石载氧体在反应过程中主要的反应以及反应后的铁矿石的床料变化。研究表明:在载氧体条件下,生物质的碳转化率显著增大,随着反应温度的升高,合成气中的H_2和CO的体积分数也相应升高。在温度不变情况下,随着水蒸气比例的升高,CO_2和H_2的体积分数显著上升。伴随着O/C摩尔比的升高,CO和H_2均显著下降。因此,在不同的反应条件下,铁矿石在生物质化学链气化过程中对反应速度、合成气比例等均有明显的作用,对研究生物质的综合利用具有一定的意义。