Characterization of La-promoted Ni/Al2O3 catalysts for hydrogen production from glycerol dry reforming

In the current paper, dry (CO₂)-reforming of glycerol, a new reforming route, was carried out over alumina (Al₂O₃)-supported, non-promoted and lanthanum-promoted nickel (Ni) catalysts. Both sets of catalysts were synthesized via a wet co-impregnation procedure. Physicochemical characterization of the catalysts showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al₂O₃ catalyst. This was also corroborated by the surface images captured by the FESEM analysis. From temperature-programmed calcination analysis, the derivative weight profiles revealed two peaks, which represent a water elimination peak at a temperature range of 373 to 473 K followed by nickel nitrate decomposition from 473 to 573 K. In addition, BET surface area measurements gave 85.0 m²·g⁻¹ for the non-promoted Ni catalyst, whilst the promoted catalysts showed an average of 1% to 6% improvement depending on the La loadings. Significantly, reaction studies at 873 K showed that glycerol dry reforming successfully produced H₂. The 2%La-Ni/Al₂O₃ catalyst, which possessed the largest BET surface area, gave an optimum H₂ generation (9.70%) at a glycerol conversion of 24.5%.     

CO2 reforming of methane over nickel catalysts supported on nanocrystalline MgAl2O4 with high surface area

In this paper dry reforming of methane (DRM) was carried out over nanocrystalline MgAl2O4-supported Ni catalysts with various Ni loadings. Nanocrystalline MgAl2O4 spinel with high specific surface area was synthesized by a co-precipitation method with the addition of pluronic P123 triblock copolymer as surfactant, and employed as catalyst support. The prepared samples were characterized by X-ray diffraction (XRD), N2 adsorption, H2 chemisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), temperature- programmed desorption (TPD) and transmission and scanning electron microscopies (TEM, SEM) techniques. The obtained results showed that the catalyst support has a nanocrystalline structure (crystal size: about 5 nm) with a high specific surface area (175 m2 g-1) and a mesoporous structure. Increasing in nickel content decreased the specific surface area and nickel dispersion. The prepared catalysts showed high catalytic activity and stability during the reaction. SEM analysis revealed that whisker type carbon deposited over the spent catalysts and increasing in nickel loading increased the amount of deposited carbon. The nickel catalyst with 7 wt% of nickel showed the highest catalytic activity.     

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al2O3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600~900 ℃ for both CO2 reforming and partial oxidation of methane. The effects of Ni loading, reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated. Catalysts of xwt%Ni/α-Al2O3 (x = 2.5, 5, 8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate. XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst, as compared with the other prepared catalyst samples. An increase of the Ni loading to more than 5 wt% led to a reduction in the Ni dispersion. In addition, by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction, the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.     

制备条件对用于甘油蒸汽重整反应Ni基催化剂性能的影响

研究了制备参数对用于甘油蒸汽重整反应的Ni基催化剂性能的影响。采用过量浸渍法、等体积浸渍法和改进的平衡沉积过滤(EDF)法制备了一系列Al2O3负载的8 wt%Ni催化剂,运用X射线衍射(XRD)、电感耦合等离子体光谱仪、N2吸附-脱附、扫描电镜(SEM)、透射电镜和H2程序升温还原(TPR)表征了催化剂的表面和体相性质;采用CHN分析仪和SEM表征了使用后催化剂以测定其表面沉积的碳及其形貌。结果表明,制备方法对所制催化剂的织构、结构和表面性质影响很大,导致氧化铝表面Ni物种的分散和种类的不同。即使XRD和TPR结果证实形成了铝酸镍晶相,但Ni/Al-edf催化剂中β峰的贡献大于其它两个催化剂的,表明在这种情况下铝酸镍更容易还原。在550 oC以上CO2选择性增加和CO选择性不变,表明Ni/Al-wet和Ni/Al-edf催化剂可成功催化水汽变换反应。另外,650oC时Ni/Al-edf催化剂上甘油生成气相产物的转化率、氢气产率以及烯丙醇、乙醛和乙酸选择性最高,且它在所有催化剂中的积炭量也最低。将催化剂结构性质、分散度和还原性与其催化性能相关联,发现EDF法制得的催化剂比表面积和活性相分散度更高,更易被还原,因而其活性和生成H2的选择性更高,也更抗积碳。     

Ni catalysts supported on nano-crystalline aluminum oxide prepared by a microemulsion method for dry reforming reaction

Mesoporous nano-crystalline γ-Al₂O₃ with high surface area prepared by a microemulsion (ME) method was employed as carrier for nickel catalysts in dry reforming of methane for syngas production. The structural properties of the catalysts were characterized by X-ray diffraction, Brunauer–Emmett–Teller surface area analysis, temperature programmed reduction and oxidation and scanning electron microscopy techniques. Microemulsion showed it to be a promising way for the production of nano-crystalline aluminum oxide, and the nickel catalysts prepared with this support have significant features and properties to use in the dry reforming reaction. The results revealed that the prepared γ-Al₂O₃ exhibited a nano-crystalline structure (crystal size: c.4.8 nm) with a high specific surface area (308 m² g^?1). In addition, the catalysts with different nickel contents exhibited high catalytic activity in the dry reforming reaction. The results also showed that an increase in Ni loading from 5 to 15 wt% caused a decrease in the specific surface area and nickel dispersion.     

Catalytic steam reforming of biomass over Ni-based catalysts: Conversion from poplar leaves to hydrogen-rich syngas

A series of Ni/SBA-15 catalysts with Ni contents from 5 wt%–20 wt%and CaO-12.5%Ni/SBA-15 catalysts with CaO contents from 1.4 wt%–9.8 wt%have been prepared.The structure of the catalysts was characterized using X-ray diffraction(XRD),N2 adsorption-desorption,transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS).The performance of catalytic steam reforming of the poplar leaves to the hydrogen-rich syngas was tested in a fixed-bed reactor.The results indicate that the 7.0wt%CaO-12.5wt%Ni/SBA-15 catalyst exhibits the best performance for the catalytic steam reforming of poplar leaves to hydrogen-rich syngas.The ratio of H2:CO can reach ca 5:1 in the hydrogen-rich syngas.The yield of H2 can reach 273.30 mL/g(poplar leaves).In the CaO-Ni/SBA-15 catalyst,Ni active component mainly fills the role of catalytic steam reforming of the poplar leaves,and CaO active component mainly plays the role as water-gas shift and CO2 sorbent.     

CO_2 reforming of glycerol over La-Ni/Al_2O_3 catalyst:A longevity evaluative study

This paper reports on the longevity of glycerol-dry(CO2) reforming over the lanthanum(La) promoted Ni/Al2O3 catalysts.The XRD results showed that the Ni particle was well-dispersed in the presence of La promoter.In addition,via the NH3-TPD analysis,it was found that the La promoter has reduced the acidity of Ni catalyst which may have explained the mitigation of carbon laydown.It was determined that the 3.0 wt% La-promoted Ni/Al2O3 catalyst possessed the largest BET specific surface area of 97 m2 g-1.Consequently,it yielded the best catalytic longevity performance with conversion attained more than 90%,even after 72 h of reaction duration.Significantly,it can be confirmed that the presence of CO2 during the glycerol dry reforming was essential in reducing carbon deposition,most likely via gasification pathway.This has ensured a stability of catalytic activity for a long reaction period(72 h).     

CO2 reforming of methane over zirconia-supported nickel catalysts, I. Catalytic specificity

CO₂ reforming of methane is performed over zirconia-supported nickel catalysts. The catalysts show high activity toward CH₄ and CO₂ conversions. Over the high Ni loading catalyst, long-term performances without significant deactivations have been achieved at 1023 K for 30 h and 1123 K for 20 h, respectively. The effects of reduction and calcination temperatures on the catalytic activities are also examined.     

Ni catalysts supported on nanocrystalline magnesium oxide for syngas production by CO2 reforming of CH4

CO2 reforming of methane (CDRM) was carried out over MgO supported Ni catalysts with various Ni loadings. The preparation of MgO supported Ni catalysts via surfactant-assisted precipitation method led to the formation of a nanocrystalline carrier for nickel catalysts. The synthesized samples were characterized by XRD, N2 adsorption-desorption, H2 chemisorption, TPR, TPO and SEM techniques. It was found that the high catalytic activity and stability of the prepared catalysts could be attributable to high dispersion of reduced Ni species and basicity of support surface. In addition, the effect of feed ratio, nickel loading and GHSV on the catalytic performance of CDRM over the catalysts were investigated.     

Effect of Ni loadings on the activity and coke formation of MgO-modified Ni/Al_2O_3 nanocatalyst in dry reforming of methane

MgO-modified Ni/Al2O3 catalysts with different Ni loadings were prepared and employed in dry reforming of methane （DRM）. The effect of Ni loadings on the activity and coke formation of Ni/MgO-A1203 catalysts were investigated. The synthesized catalysts were characterized by XRD, N2 adsorption-desorption, SEM, TPO and TPR techniques. The obtained results showed that increasing nickel loading decreased the BET surface area and increased the catalytic activity and amount of deposited carbon. In addition, the effect of gas hourly space velocity （GHSV） and feed ratio were studied.     

Studies on the Adsorption and Dissociation of Methane and Carbon Dioxide on Nickel

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalysts were extensively investigated by TPSR, TPD, XPS and pulse reaction methods. These studies showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalysts. Carbidic Cα, carbonaceous Cβ and carbidic clusters Cγ surface carbon species formed by the decomposition of methane demonstrated different surface mobility, thermal stability and reactivity. Carbidic Cα is a very active and important intermediate in carbon dioxide reforming with methane, and the carbidic clusters Cγ species might be the precursor of surface carbon deposition. The partially dehydrogenated Cβ species can react with H2 or CO2 to form CH4 or CO. On the other hand, it was proven that CO2 can be weakly adsorbed on supported nickel catalysts, and only one kind of CO2 adsorption state is formed. The interaction mechanism between the species dissociated from CH4 and CO2 during reforming was then hypothesized.     

镍基催化剂上乙醇水蒸气重整反应的研究

考察了载体对Ni催化剂乙醇水蒸气重整制氢反应性能的影响。结果表明，Ni/CeO2催化剂具有较好的低温活性和氢气选择性。对Ni担载量和焙烧温度考察发现，400℃焙烧的15%NiCeO2催化剂具有较好的催化性能；继续升高焙烧温度引起NiO和CeO2粒子的显著增大,导致对氢气选择性的降低。较小的Ni和CeO2粒子有利于乙醇水汽重整反应的进行，而大的粒子倾向于乙醇的分解反应。 350℃时,在反应过程中分别添加CO、CO2和CH4的结果表明没有发生CO和CO2甲烷化反应,而发生了一定程度的CH4水汽重整反应。     

La-Ni-Al钙钛矿氧化物中Sr和Ca取代La对甲醇重整的影响

Mixed perovskite oxides with CaxLa1-xNi0.3Al0.7O3-d and SrxLa1-xNi0.3Al0.7O3-d(x=0,0.2,0.5,0.8,and 1.0;d=0.5x)components have been prepared by a sol-gel method.The effects of the partial substitution of La by Ca and Sr in dry CH4 reforming were investigated at 500-800 ℃ and 101 kPa.The resulting oxides were examined by Fourier-transform infrared spectroscopy,X-ray diffraction,temperature-programmed reduction,scanning electron microscopy,energy dispersive X-ray spectrometry,and BET surface area analysis.Studies following the catalytic tests by carbon analysis show some carbon deposition on this catalytic system.The results indicate that all initial salt entered into a propionate structure,and that most of the solid solution has well defined perovskite structure with surface areas between 3.5 and 9.5 m2/g.Most of the catalysts performed well in the dry reforming,with CH4 conversions up to 90%,H2 yields up to 80%,and H2 selectivity up to 90%.Among the samples,Sr0.2La0.8Ni0.3Al0.7O2.9 showed an excellent catalytic performance in CH4 dry reforming,with a H2/CO ratio of 1,whereas Ca0.8La0.2Ni0.3Al0.7O2.6 showed the lowest coke formation(approximately 0.71%).     

Comparison of dry reforming of methane in low temperature hybrid plasma-catalytic corona with thermal catalytic reactor over Ni/γ-Al2O3

In the current study,the hybrid effect of a corona discharge and γ-alumina supported Ni catalysts in CO2 reforming of methane is investigated.The study includes both purely catalytic operation in the temperature range of 923-1023K,and hybrid catalytic-plasma operation of DC corona discharge reactor at room temperature and ambient pressure.The effect of feed flow rate,discharge power and Ni/γ-Al2O3 catalysts are studied.When CH4/CO2 ratio in the feed is 1/2,the syngas of low H2/CO ratio at about 0.56 is obtained,which is a potential feedstock for synthesis of liquid hydrocarbons.Although Ni catalyst is only active above 573K,presence of Ni catalysts in the cold corona plasma reactor(T≤523K) shows promising increase in the conversions of methane and carbon dioxide.When Ni catalysts are used in the plasma reaction,H2/CO ratios in the products are slightly modified,selectivity to CO increases whereas fewer by-products such as hydrocarbons and oxygenates are formed.     

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 Ni Loading and CexZr1-xO2 Promoter on Ni-Based SBA-15 Catalysts for Steam Reforming of Methane

A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt?xZn-xO2/SBA-15 (z=0, 0.5, 1) were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at atmospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800癈 for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.     

低镍催化剂上CO和CO_2加氢反应的对比研究

采用ＣＯ和ＣＯ＿２对比加氢活性测试，ＸＲＤ及ＴＰＲ方法研究了两个不同Ｎａ助剂含量的低镍Ｎｉ／Ａｌ＿２Ｏ＿３体系的性能。实验发现，在低镍催化剂上ＣＯ＿２在较低温度下就可加氢生成甲烷，而ＣＯ则需要更高的温度，ＣＯ＿２无需先经逆变换生成ＣＯ，然后再加氢，它可直接加氢生成ＣＨ＿４。在同一催化剂上，ＣＯ＿２加氢生成ＣＨ＿４的表现活化能要低于ＣＯ加氢生成ＣＨ＿４反应的表现活化能。晶相ＮｉＯ还原后形成的活性相对ＣＯ＿２加氢反应的活性明显高于它对ＣＯ的加氢活性，非晶相镍氧化物还原后形成的活性相对ＣＯ的加氢反应特别有利。Ｎａ助剂的含量不同会造成Ｎｉ氧化物物种的分配不同，从而导致ＣＯ、ＣＯ＿２的加氢活性及其随温度的变化也不相同，催化剂对ＣＯ、ＣＯ＿２加氢反应作用的本质是不相同的。     

制备方法对Ni/ZnO催化丙三醇重整-氢解性能的影响

采用浸渍法、共沉淀法、水热法和碳微球硬模板法制备了Ni/ZnO催化剂,运用X射线衍射、程序升温还原、透射电子显微镜和氢滴定等手段对其进行了表征,并用于连续固定床反应器中无外加氢气条件下的丙三醇重整-氢解反应.结果表明,在较低空速下,生成的1,2-丙二醇(1,2-PDO)易在Ni分散度较高的催化剂上进一步裂解为乙醇和气相产物;而在较高空速下,其选择性受制于中间产物丙酮醇的加氢.在优化的空速下,Ni分散度越高越有利于1,2-PDO的生成.在Ni分散度最高的Ni/ZnO催化剂上,当丙三醇质量空速为0.84h-1时,1,2-PDO选择性最高,为54.9%,丙三醇转化率为85.4%.     

Effect of O2 and H2O on the tri-reforming of the simulated biogas to syngas over Ni-based SBA-15 catalysts

A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method. The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor. The stability of the catalyst was tested at 800 ℃. The results indicated that 10 wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas. Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6, GHSV = 24000 ml•g{cat}-1\cdoth-1 and the reaction temperatureT = 800 ℃, the conversions of CH4 and CO2 were 92.8% and 76.3%, respectively, and the yields of CO and H2 were 99.0% and 82.0%, respectively. The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.     

CO2重整CH4纳米ZrO2负载Ni催化剂的研究(Ⅱ)──催化剂组成与反应条件对催化剂性能的影响

研究了粒径为15～18nm的纳米ZrO₂-AS负载Ni催化剂对CO₂重整CH₄制合成气的催化性能,结果表明,Ni/ZrO₂-AS催化剂对重整反应的超常稳定催化作用不受Ni含量的影响,但当Ni质量分数低于10%时,催化剂活性随Ni含量增加而显著上升,此后,CH₄和CO₂的转化逐渐接近其热力学平衡值.高空速虽然降低了反应物的转化率,但可得到更高的时空产率.各种表征数据揭示,Ni/ZrO₂在结构上有别于传统的负载型催化剂,可看成是由尺寸相当(10～20nm)的纳米金属Ni和纳米ZrO₂形成的纳米复合物催化剂.