煤与甲烷共转化过程中煤焦二氧化碳气化动力学研究

以煤与甲烷共转化为背景,运用热重方法进行了由煤焦、甲烷和二氧化碳组成的共转化反应体系中碳的反应动力学研究。在1173K~1273K考察了温度对碳转化的影响。结果表明,该反应体系中碳的表观反应速率比煤焦的纯二氧化碳气化速率慢一倍左右,且表观上碳不能完全被气化。通过改变甲烷和二氧化碳的比例考察了气相组成变化对共转化反应中碳转化速率的影响,发现甲烷浓度的增加和二氧化碳浓度的减少都会降低碳的转化速率,且随着甲烷浓度的增加,表观上碳最终所能达到的转化率也会降低。通过数据分析发现,该反应适合采用均相反应模型进行描述,关联得到其表观活化能为312.4kJ/mol,甲烷的反应级数为-0.13,二氧化碳的反应级数为0.3。     

甲烷二氧化碳转化制备富含一氧化碳合成气

研究了甲烷二氧化碳转化反应的热力学特性,计算了反应平衡常数及平衡组成,分析和确定了抑制积碳的生成条件,采用固定床流动和脉冲反应装置研究了Ni/Al_2O_3催化剂对甲烷二氧化碳转化的催化性能。     

甲烷在褐煤煤焦上的裂解反应研究

采用石英管固定床反应器,分别考察了不同温度（1123K、1173K、1223K、1273K）及不同浓度（10%、15%、20%）下,甲烷在褐煤煤焦上的裂解反应。结果表明,褐煤煤焦对甲烷裂解反应具有良好的催化活性,在所考察温度范围内,甲烷的初始转化率最高达99.5%,温度越高,甲烷的初始转化率越高;但随着反应的进行,转化率逐渐降低;甲烷进气浓度越高,初始转化率越低,而且催化剂失活也越快。反应前后煤焦电镜扫描照片及物性参数的比较表明,甲烷裂解生成炭沉积在煤焦表面,导致煤焦比表面积随反应的进行逐渐降低,与甲烷裂解转化率的变化趋势一致;反应后煤焦的孔容及微孔容都有所降低,平均孔径增大,说明甲烷的裂解生成炭造成了煤焦孔道尤其是微孔的堵塞,比表面积减小,导致了甲烷的转化率降低。     

甲烷与二氧化碳重整制取合成气反应的研究

合成了具有磁铅石结构的Ｓｒ１－ｘＬａｘＮｉＡｌ１１Ｏ１９系列催化剂，并用ＸＲＤ、ＵＶ－ＤＲＳ、Ｈ２－Ｏ２滴定及Ｐｙ－ＩＲ等方法对其体相及表面性质进行了表征，结果表明，Ｌａ＾３＋离子能够同晶取代Ｓｒ＾２＋离子进入催化剂晶格内部；随着Ｌａ＾２＋含量增加，催化剂的结晶度提高，从而降低了镍的还原性，并使金属镍的表面上的分散度略有提高，在ＳｒＮｉＡｌ１１Ｏ１９中掺入Ｌａ＾３＋离子，能够抑制晶体沿ｃ轴方向的生     

负载碳酸钾煤焦上CO甲烷化反应的研究

在加压固定床反应器中,考察了负载碳酸钾的府谷煤热解半焦和不同气化率的部分气化半焦对CO甲烷化反应的催化性能。结果表明,原煤热解半焦和脱灰煤热解半焦的甲烷化活性都很低,而负载10%(质量分数)碳酸钾的热解半焦甲烷化活性明显提高,甲烷收率可达30%。负载碳酸钾的热解半焦水蒸气气化反应速率与碳气化率呈"火山"型关系曲线,在碳气化率为22%时达到极大值。在气化反应速率较高时得到的部分气化半焦上,甲烷化反应速率较低。利用红外光谱对半焦官能团进行分析,发现在热解过程中,碳酸钾和煤发生反应形成C-O-K复合物,在1100 cm-1附近出现特征振动峰,该峰的强度与碳气化反应速率成正比。不同气化率半焦经过甲烷化反应后,红外光谱谱图中C-O-K峰强度不同程度增大。     

甲烷催化二氧化碳重整制合成气反应研究进展*

本文参阅了甲烷催化二氧化碳重整制合成气反应研究方面50 余篇文献, 概述了近年来在该研究中催化剂活性组分选择、载体效应、助剂的作用、催化剂积炭行为和重整反应机理等方面的研究进展。     

Ni／Al2O3上甲烷二氧化碳氧气转化制备合成气的研究

在固定床流动反应装置上，从活性组分的负载量，载体的焙烧温度、反应温度，空速等几个方面考察了Ｎｉ／Ａｌ２Ｏ３催化剂对ＣＨ４－ＣＯ２－Ｏ２转化制备合成气的催化活性，发现采用１１００℃焙烧的γ－Ａｌ２Ｏ３载体制备的镍负载量为９．１７ｗ％的Ｎｉ／Ａｌ２Ｏ３催化剂。     

甲烷／二氧化碳重整反应催化剂的制备及反应性能研究

采用浸渍法制备载镍ＣＨ４／ＣＯ２重整反应催化剂，应用ＩＣＰ，ＢＥＴ，ＥＰＭＡ，ＳＥＭ，ＴＥＭ，ＸＰＳ等手段考察了焙烧温度，浸渍液酸度，助剂等制备条件对催化剂结构及反应性能的影响。结果表明，低温热处理制备的Ｎｉ／γ－Ａｌ２Ｏ３催化剂具有较高的ＣＨ４／ＣＯ２重整反应活性．经酸或强碱溶液中制备的催化剂尽管活性分布及孔结构等均扔所不同，但二者的反应活性都很高；     

褐煤热解过程中半焦重整催化剂性质的变化

为降低焦油产率,提高褐煤气化效率,采用胜利褐煤热解所得的半焦作为催化剂,在二阶石英反应器中对煤热解的焦油进行原位催化重整,分析和讨论了反应前后半焦催化剂的性质变化。结果表明,反应后半焦质量较反应前普遍有所下降,半焦是一种消耗性催化剂;反应后半焦的比表面积由422 m~2/g降到231.8 m~2/g;Raman分析结果表明,反应后半焦含氧官能团、小环(3-5个缩合芳环)与大环(大于5个缩合芳环)体系之比均有所降低。在半焦-挥发分作用过程中,快速热解制得半焦主要将挥发分裂解为小分子气体,慢速热解制得的半焦则主要使挥发分缩聚结焦脱除。     

Sorption of methane and CO2 for enhanced coalbed methane recovery and carbon dioxide sequestration

Sequestration of CO2 in deep and unmineable coal seams is one of the attractive alternatives to reduce its atmospheric concentration. Injection of CO2 in coal seams may help in enhancing the recovery of coalbed methane. An experimental study has been carried out using coal samples from three different coal seams, to evaluate the enhanced gas recovery and sequestration potential of these coals. The coals were first saturated with methane and then by depressurization some of the adsorbed methane was desorbed. After partial desorption, CO2 was injected into the coals and subsequently they were depressurized again. Desorption of methane after the injections was studied, to investigate the ability of CO2 to displace and enhance the recovery of methane from the coals. The coals exhibited varying behavior of adsorption of CO2 and release of methane. For one coal, the release of methane was enhanced by injection of CO2, suggesting preferential adsorption of CO2 and desorption of methane. For the other two coals, CO2 injection did not produce incremental methane initially, as there was initial resistance to methane release. However with continued CO2 injection, most of the remaining methane was produced. The study suggested that preferential sorption behavior of coal and enhanced gas recovery pattern could not be generalized for all coals.     

Sorption of methane and CO2 for enhanced coalbed methane recovery and carbon dioxide seauestration

Sequestration of CO2 in deep and unmineable coal seams is one of the attractive alternatives to reduce its atmospheric concentration. Injection of CO2 in coal seams may help in enhancing the recovery of coalbed methane. An experimental study has been carried out using coal samples from three different coal seams, to evaluate the enhanced gas recovery and sequestration potential of these coals. The coals were first saturated with methane and then by depressurization some of the adsorbed methane was desorbed. After partial desorption, CO2 was injected into the coals and subsequently they were depressurized again. Desorption of methane after the injections was studied, to investigate the ability of CO2 to displace and enhance the recovery of methane from the coals. The coals exhibited varying behavior of adsorption of CO2 and release of methane. For one coal, the release of methane was enhanced by injection of CO2, suggesting preferential adsorption of CO2 and desorption of methane. For the other two coals, CO2 injection did not produce incremental methane initially, as there was initial resistance to methane release. However with continued CO2 injection, most of the remaining methane was produced. The study suggested that preferential sorption behavior of coal and enhanced gas recovery pattern could not be generalized for all coals.     

Effect of metal oxides on the reforming of methane with carbon dioxide

The effect of basic and rare earth metal oxides on the stability of nickel-based catalysts for the CO₂ reforming of CH₄ has been studied. The addition of metal oxides increased the stability of Ni-based catalysts and reversed the values of the reaction orders with respect to both CH₄ and CO₂. In the presence of metal oxides, the values of the reaction orders with respect to CO₂ partial pressure followed the same trend of catalyst stability.     

Ni-Mg-ZrO2催化剂上煤层甲烷三重整制合成气

采用共沉淀法制备Ni-ZrO₂和Ni-Mg-ZrO₂催化剂,用BET、XRD、H₂-TPR、CO₂-TPD等技术对催化剂进行了表征。采用固定床流动反应装置,研究了催化剂在煤层甲烷三重整制合成气反应中的催化性能;考察了反应温度和原料气体组成对反应的影响。实验结果表明,Ni-Mg-ZrO₂催化剂在反应温度800℃、常压、空速为30 000 mL/(g·h)、CH₄/CO₂/H₂O/O₂/N₂=1.0/0.45/0.45/0.1/0.4的条件下,CH₄转化率为99%,CO₂转化率为65%左右,生成合成气H₂/CO体积比为1.5,并在58 h的实验中催化剂活性和稳定性良好。这主要归因于催化剂中金属和载体之间的强相互作用、催化剂的高热稳定性和强碱性。此外,较高的反应温度有利于甲烷三重整反应的进行;通过调节原料气组成,可以获得不同H₂/CO体积比的合成气。     

钙钛矿型氧化物负载Ni催化剂上甲烷二氧化碳重整反应研究

采用浸渍法制备了一系列MTiO₃(M=Mg、Ca、Sr、Ba)钙钛矿型氧化物负载的Ni催化剂(Ni的负载量为5%,质量分数),通过XRD、氮吸附、H₂-TPR、CO₂-TPD、XPS和TG等技术对催化剂进行了表征,对其甲烷二氧化碳重整反应的催化性能进行了研究。结果表明,M为不同碱土金属时,催化剂上金属载体相互作用、活性组分的表面原子浓度以及催化剂晶格氧的流动性都发生了变化。Ni/CaTiO₃催化剂上金属载体相互作用较强,还原出的活性组分Ni的含量较多,晶格氧流动性较高,因而具有较好的催化性能。SrTiO₃载体颗粒粒径较大,Ni/SrTiO₃催化剂上Ni的分散度不高,金属载体的相互作用较弱,表面Ni原子相对含量较低,晶格氧的流动性较差,其甲烷二氧化碳重整反应活性也最低。     

Ni-La/CexZr1-xO2对甲烷部分氧化/CH4-CO2重整耦合制合成气的催化剂制备及反应性能

通过共沉淀法制备铈锆固溶体作为载体,采用等体积、分步浸渍的方法制备了一系列10% Ni-3% La/CexZr1-xO2（X=0、0.16、0.5、0.75、1）催化剂,并将其应用到甲烷部分氧化和甲烷二氧化碳重整耦合制合成气的反应中。对不同Ce/Zr比的催化剂性能展开研究,采用XRD、H2-TPR、SEM手段对载体及催化剂进行了表征。结果表明,铈锆固溶体的形成不仅提高了催化剂表面活性组分的分散度,使催化剂表面NiO晶粒尺寸从26.5 nm减到13.7 nm;而且能够加强活性组分与载体之间的相互作用,提高催化剂的热稳定性能;随着Ce/Zr比的增加,催化剂的转化率、选择性及稳定性随之增强,其关系为：Ni-La/Ce0.75Zr0.25O2 > Ni-La/Ce0.5Zr0.5O2 > Ni-La/Ce0.16Zr0.84O2。     

Ultra-stable Ni catalysts for methane reforming by carbon dioxide

Methane reforming by carbon dioxide has been studied over ultra-stable Ni catalysts. The catalyst was characterized by XRD, IR and TEM and temperature programmed hydrogenation. The nickel–magnesia solid solution catalyst containing low nickel has shown excellent stability (>3000 h) and no carbon deposition in the methane reforming by carbon dioxide. It was also found that the small nickel metal particle interaction with support surface is effective for the inhibition of carbon formation.