CO selective methanation in hydrogen-rich gas mixtures over carbon nanotube supported Ru-based catalysts

Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure.It was found that the metal promoter,reduction temperature and metal loading affected the catalytic properties significantly.The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350℃.Since it decreased CO concentration to below 10ppm from 12000ppm by CO selective methanation at the temperature range of 180-240℃,and kept CO selectivity higher than 85% at the temperature below 200℃.Characterization using XRD,TEM,H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs,a higher Ru dispersion and the oxidization of surface Ru.Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350℃,leading to excellent catalytic performance in CO selective methanation.     

Highly selective CO methanation over amorphous Ni-Ru-B/ZrO_2 catalyst

Amorphous Ni-Ru-B/ZrO_2 catalyst was prepared by the means of chemical reduction,and selective CO methanation as a strategy for CO removal in fuel processing applications was investigated over the amorphous Ni-Ru-B/ZrO_2 catalyst.The result showed that,at the temperature of 210-230℃,the catalyst was shown to be capable of reducing CO in a hydrogen-rich reformate to less than 10 ppm,while keeping the CO_2 conversion below 1.55%and the hydrogen consumption below 6.50%.     

Selective catalytic methanation of CO in hydrogen-rich gases over Ni/ZrO2 catalyst

Ni/ZrO2 catalysts were prepared by the incipient-wetness impregnation method and were investigated in activity and selectivity for the selective catalytic methanation of CO in hydrogen-rich gases with more than 20 vol% CO2. The result showed that Ni loadings significantly influenced the performance of Ni/ZrO2 catalyst. The 1.6 wt% Ni loading catalyst exhibited the highest catalytic activity among all the catalysts in the selective methanation of CO in hydrogen-rich gas. The outlet concentration of CO was less than 20 ppm with the hydrogen consumption below 7%, at a gas-hourly-space velocity as high as 10000 h-1 and a temperature range of 260 °C to 280 °C. The X-ray diffraction （XRD） and temperature programmed reduction （TPR） measurements showed that NiO was dispersed thoroughly on the surface of ZrO2 support if Ni loading was under 1.6 wt%. When Ni loading was increased to 3 wt% or above, the free bulk NiO species began to assemble, which was not favorable to increase the selectivity of the catalyst.     

Effect of decomposition of catalyst precursor on Ni/CeO2 activity for CO methanation

CO methanation on Ni/CeO₂ has recently received increasing attention. However, the low-temperature activity and carbon resistance of Ni/CeO₂ still need to be improved. In this study, plasma decomposition of nickel nitrate was performed at ca. 150°C and atmospheric pressure. This was followed by hydrogen reduction at 500 °C in the absence of plasma, and a highly dispersed Ni/CeO₂ catalyst was obtained with improved CO adsorption and enhanced metal-support interaction. The plasma-decomposed catalyst showed significantly improved low-temperature activity with high methane selectivity (up to 100%) and enhanced carbon resistance for CO methanation. For example, at 250°C, the plasma-decomposed catalyst showed a CO conversion of 96.8% with high methane selectivity (almost 100%), whereas the CO conversion was only 14.7% for a thermally decomposed catalyst.     

Removal of CO from reformed fuels by selective methanation over Ni-B-Zr-Oδ catalysts

The Ni-B-Oδ andNi-B-Zr-Oδ catalysts were prepared by the method of chemical reduction, and the deep removal of CO by selective methanation from the reformed fuels was performed over the as-prepared catalysts. The results showed that zirconium strongly influenced the activity and selectivity of the Ni-B-Zr-Oδ catalysts. Over the Ni-B-Oδ catalyst, the highest CO conversion obtained was only 24.32% under the experimental conditions studied. However, over the Ni-B-Zr-Oδ catalysts, the CO methanation conversion was higher than 90% when the temperature was increased to 220 oC. Additionally, it was found that the Ni/B mole ratio also affected the performance of the Ni-B-Zr-Oδ catalysts. With the increase of the Ni/B mole ratio from 1.8 to 2.2, the CO methanation activity of the catalyst was improved. But when the Ni/B mole ratio was higher than 2.2, the performance of the catalyst for CO selective methanation decreased instead. Among all the catalysts, the Ni29B13Zr58Oδ catalyst investigated here exhibited the highest catalytic performance for the CO selective methanation, which was capable of reducing the CO outlet concentration to less than 40 ppm from the feed gases stream in the temperature range of 230–250 oC, while the CO2 conversion was kept below 8% all along. Characterization of the Ni-B-Oδ and Ni-B-Zr-Oδ catalysts was provided by XRD, SEM, DSC, and XPS.     

褐煤煤焦“一步法”制天然气双功能催化剂Fe-Ni/ATP性能研究

以Fe-Ni/ATP为催化剂,在小型固定床反应器上考察其在褐煤煤焦"一步法"制天然气过程中的催化性能。结果表明,在2 MPa、650℃反应条件下,Fe4Ni2/ATP4具有较好的催化气化和甲烷化性能,甲烷选择性为24.75%,较Fe4/ATP6的选择性提高了58.76%;且在五次循环实验过程中,碳转化率和CH4时空产率保持稳定,具有较高的稳定性。载体ATP中的CaO具有明显的气化催化效果;Fe与水蒸气反应生成的H2可快速提高反应器内H2分压,促进煤焦直接加氢甲烷化和CO甲烷化;Ni降低了催化剂的还原温度并形成铁镍合金活性组分,提高了催化剂的甲烷化催化性能。     

液相中镍催化剂催化合成气甲烷化的初步研究

采用液相还原法制备非负载型镍催化剂,将非负载型镍催化剂分散在液相供氢溶剂十氢萘中,催化合成气甲烷化反应。在高压反应釜内,考察了反应温度、物质的量比等操作条件下,镍催化剂催化合成气甲烷化反应的反应活性。并对催化剂进行XRD、SEM、H2-TPR表征分析。研究结果表明,在330℃、催化剂用量为2%时,产品气中甲烷含量可达89.39%,CO和H2的转化率分别为94.56%和92.60%;催化剂用量为4%时,产品气中甲烷含量可高达94.26%,CO的转化率可达到99%以上。合成气甲烷化反应的最佳操作温度为330℃,H2/CO物质的量比最佳为2.20~2.67。     

泡沫金属微反应器内富氢重整气中CO选择性甲烷化

在微反应器中,用泡沫金属镍为载体负载4Ni-2Ru/ZrO2双金属催化剂,用于选择性甲烷化去除富氢重整气中的CO。考察了催化剂负载方法、焙烧温度和空速等对CO选择性甲烷化的影响,借助X射线衍射(XRD)、程序升温还原(H2-TPR)等手段对催化剂制备方法与催化性能的关系进行了探讨。结果表明,直接将4Ni-2Ru/ZrO2催化剂涂布在泡沫镍片上,350℃下焙烧,反应温度为260℃,空速为2 000 h-1~6 000 h-1,可将富氢转化气中CO降至30×10-6以下,其中空速为5 000 h-1,可将CO出口浓度降至7×10-6,CO2的转化率低于1.5%。反应温度在260℃~300℃,CO的转化率在99.6%以上,CO出口浓度在50×10-6以下。     

不同载体Ni基催化剂生物质热解气甲烷化反应性能

采用浸渍法制备了Ni金属负载在不同载体(SiO2、ZrO2、CeO2、Al2O3和Al2O3-CeO2)表面形成的催化剂,研究了水蒸气和载体对生物质热解气甲烷化反应性能的影响。结果表明,随着水蒸气量的增加CO转化率逐渐增大,而甲烷选择性呈现先增加后降低的变化趋势,当nw ater/ngas比值为0.26时达到最大。载体Al2O3相比SiO2、ZrO2和CeO2具有更大的比表面积和Ni金属分散度,促进了生物质热解气甲烷化反应活性和选择性。相比于Ni-Al2O3催化剂,Al2O3-CeO2复合载体具有更多的镍金属负载量活性金属分散度,以及最好的低温甲烷化反应性能。在300℃的低温条件下,Ni-Al2O3-CeO2催化剂的CO转化率达到97%,CH4增长率达到110%。     

共沉淀浸渍法制备由合成气直接合成二甲醚的Cu-Mn催化剂

采用共沉淀浸渍法,制备了直接合成二甲醚的Cu-Mn-Zn催化剂,通过对组成成分及其配比的研究,发现Cu含量一定的条件下,n(Zn)/n(Mn)摩尔比对催化剂性能有较大的影响,当n(Zn)/n(Mn)=1/3～1/2时,催化剂对CO的转化率和对二甲醚的选择性达到最佳,分别为53.6%和63.5%；如锰添加比例过大,对催化剂催化合成二甲醚有微弱抑制；添加锌比例过大,会大大降低CO的转化率。载体Y分子筛的含量对催化剂性能也有影响,用量过大将降低催化剂的活性和对二甲醚的选择性,当其含量为33%时,催化剂上CO转化率和选择性可分别达到66%和68%,且催化剂活性随分子筛含量减少不再有明显的变化。     

Ni/ZrO2催化剂上甲烷水蒸气重整反应的研究

研究了Ni/ZrO2催化剂对甲烷水蒸气重整制合成气的反应性能。考察了催化剂的还原温度、载体焙烧温度以及反应温度、原料配比和空速等对催化剂性能的影响。利用XRD、TEM、XPS等手段对催化剂的织构形貌进行了表征。研究表明，Ni/ZrO2催化剂用于甲烷水蒸气重整制合成气不仅具有较高的活性，也具有较好的稳定性。水蒸气比增加，CH4转化率增大、CO选择性下降。CH4转化率及CO选择性均随空速增大而下降。使用10%Ni/ZrO2催化剂，在650 ℃、空速1.984×104 h－1、原料气配比H2O∶CH4∶N2=2∶1∶2.67的条件下，获得CH4转化率85%、CO选择性70%的结果。     

焙烧条件对浆态床CO甲烷化Ni-Al2O3催化剂性能的影响

结合行星式球磨机,采用机械化学法制备Ni-Al₂O₃催化剂,考察了焙烧温度和焙烧时间对Ni-Al₂O₃催化剂晶相结构、还原特征、孔道结构和浆态床CO甲烷化性能的影响。通过XRD、H₂-TPR、BET、XPS和TPH等方法对反应前后催化剂进行表征。结果表明,焙烧温度从350℃升高到700℃,活性前体NiO仍在载体表面高度分散,催化剂还原峰温向高温方向偏移。其中,450℃条件下焙烧所获得的cat-450试样比表面积最大,为350 m²/g。评价结果显示,焙烧温度从350℃升高到700℃,CO转化率、CH₄选择性和收率均呈先升高后降低的趋势,于450℃达到最大值,分别为97.8%、88.2%和86.2%。另外,焙烧时间对催化剂的还原性能影响较小,对载体Al₂O₃的晶相结构有一定影响。随焙烧时间延长,CO转化率稍有降低,而后增大;焙烧时间为4 h,CH₄选择性和收率均较大。     

Selective methanation of CO in the presence of CO<Subscript>2</Subscript> in hydrogen-containing mixtures on nickel catalysts

The screening of commercial nickel catalysts for methanation and a series of nickel catalysts supported on CeO₂, γ-Al₂O₃, and ZrO₂ in the reaction of selective CO methanation in the presence of CO₂ in hydrogen-containing mixtures (1.5 vol % CO, 20 vol % CO₂, 10 vol % H₂O, and the balance H₂) was performed at the flow rate WHSV = 26000 cm³ (g Cat)⁻¹ h⁻¹. It was found that commercial catalytic systems like NKM-2A and NKM-4A (NIAP-07-02) were insufficiently effective for the selective removal of CO to a level of <100 ppm. The most promising catalyst is 2 wt % Ni/CeO₂. This catalyst decreased the concentration of CO from 1.5 vol % to 100 ppm in the presence of 20 vol % CO₂ in the temperature range of 280–360°C at a selectivity of >40%, and it retained its activity even after contact with air. The minimum outlet CO concentration of 10 ppm at 80% selectivity on a 2 wt % Ni/CeO₂ catalyst was reached at a temperature of 300°C.     

碳纳米管负载Cu-Co复合氧化物的富氢气氛中CO催化消除

采用超声处理辅助浸渍法制备了多壁碳纳米管负载的Cu-Co复合氧化物催化剂. 利用XRD、TEM、H2-TPR、XPS和Raman光谱等表征了催化剂的结构性质. 在Cu和Co氧化物以及金属氧化物与碳纳米管载体间存在强相互作用. 催化剂在富氢气氛中CO催化消除反应中,与单一Cu或Co催化剂相比,Cu-Co复合氧化物催化剂表现出独特的反应特性,特别是在较高反应温度下可同时结合CO优先氧化和CO甲烷化的反应途径来实现高效CO消除. 当Cu/Co比为1/8时活性最优,可以实现在150-250℃和高反应空速 （120 L/（h·g））富氢气氛中CO的完全消除.     

含氧煤层气流化床催化燃烧脱氧特性研究

利用自制的铜基球形甲烷催化燃烧催化剂,在小型流化床反应器中对模拟含氧煤层气进行了流化床催化燃烧脱氧的实验研究,考察了床层温度、催化剂粒径、空速对脱氧效率和CO₂选择性的影响。结果表明,较高的反应床层温度使催化剂活性增强,进而提高催化脱氧效率。床层温度在450 ℃以上,脱氧效率可稳定保持在95%以上。较小的催化剂粒径降低了内扩散阻力对催化反应的影响,提高催化反应的CO₂选择性。床层温度在450 ℃以下时,降低空速可提高氧气转化率,但温度高于450 ℃时,脱氧反应速率加快,空速变化对脱氧效率影响不明显。此外,通过调节CH₄/Air比例模拟不同含氧量的煤层气,考察流化床反应器及催化剂对含氧煤层气中O₂浓度变化的适应性。模拟含氧煤层气中氧气体积分数在5%~15%,该催化剂均表现出高的脱氧活性和选择性,反应器出口气体中氧气体积分数低于0.2%,CO₂选择性高于98%。     

Pt/Al2O3整体催化剂上选择性氧化脱除甲醇重整氢源中CO --副反应对CO脱除效果的影响分析

移动甲醇重整制氢是质子交换膜燃料电池（PEMFC）可行的供氢方式之一,包括水蒸气重整、部分氧化重整和自热重整。甲醇重整制氢方法不同,重整气体积组成在H245％～75％,CO215％～25％,CO1％～10％,H2O10％～20％和N20—20％变化。重整气进入PEMFC之前要经过CO水蒸气变换反应（如果采用水蒸气重整,不需要变换过程）,     

甲烷部分氧化Ni催化剂及助剂的研究

考察了不同Ni担载量的Ni／a－Al_2O_3催化剂的催化性能，以8％Ni（质量分数）最佳．XRD分析表明，8％Ni催化剂表面NiO颗粒最小．TPR分析表明，催化剂表面主要有两种不同化学环境的NiO，当Ni担载量超过12％时，表面开始出现“游离态”NiO，这部分NiO易使催化剂积碳．添加稀土Ce有利于提高Ni催化剂的活性、选择性和稳定性，并对Ce的助剂效应作了研究．     

Rh/NaY催化剂上合成气选择一步生成乙酸

在合成气(CO+H₂)催化转化反应中,含适当助剂(如Mn、Fe、V等)的负载型Rh催化剂能够有选择地催化生成C₂含氧化合物,某些氧化物载体本身也会成为Rh催化剂的助剂^[1～3].     

Zr改性Ni/γ-Al2O3催化剂用于浆态相合成气的低温甲烷化

采用浆态床反应器,在低温(300~330 ℃)下进行合成气的甲烷化反应.实验中通过共浸渍法(包括含浸-旋蒸法)制备了锆(Zr)修饰的Ni/γ-Al₂O₃催化剂,并考察其与单一NiO、未掺杂Zr 的Ni/γ-Al₂O₃催化剂的催化性能差异.研究表明,载体γ-Al₂O₃的引入能够明显地提高CO的转化率和甲烷的选择性,而Zr的掺杂会进一步提升催化剂的催化活性.在325 ℃,空速为4 200 mL·g^-1·h^-1时,CO的转化率可以达到86.41%,甲烷选择性为90.53%.催化剂的表征结果表明,Zr的添加促进了Ni在催化剂表面的分散、减弱了活性Ni与载体的相互作用,抑制了低甲烷化活性的NiAl₂O₄的生成,使得催化剂的反应性能得到较大提高.     

CeO2的形貌特征对Ni/CeO2催化剂CO甲烷化性能的影响

通过改变制备方法合成了不同形貌的CeO_2载体(包括球状CeO_2-S、花苞状CeO_2-F和多面体状CeO_2-P),并用氨水配位浸渍法制备了Ni/CeO_2催化剂。研究了CeO_2载体结构与Ni/CeO_2催化剂上CO甲烷化反应性能的关系。结果表明,CeO_2-S、CeO_2-F和CeO_2-P载体暴露的晶面和氧空位不同,对Ni/CeO_2催化剂催化活性影响也不相同。CeO_2-S氧空位最多,Ni/CeO_2-S在350℃下CO转化率和CH4选择性分别达到99.19%和88.88%。10 h热稳定性测试结果表明,Ni/CeO_2-S催化剂上的积炭量最少(2.5%),CH4选择性一直保持在80%左右,分别是Ni/CeO_2-F的1.3倍和Ni/CeO_2-P的17.6倍。这主要归因于CeO_2-S载体比表面积较大,主要暴露[111]晶面,且表面氧空位含量较多,使Ni/CeO_2-S催化剂的载体与活性中心的相互作用增强,从而呈现出优异的抗积炭性能。