Ni-based catalysts obtained from perovskites oxides for ethanol steam reforming

Perovskites as host structures of cations were used in order to generate in situ active and stable catalysts for ethanol steam reforming. For this purpose, La_1-xMg_xAl_1-yNi_yO₃ (x = 0.1; y= 0, 0.1, 0.2, 0.3) perovskites were synthetized by the citrate method. Ni segregation is evident for a substitution level higher than 0.2. The segregation of Ni as NiO generated species interacts with different metal-support after the reduction step. The y= 0.1 catalyst presents the highest H₂ yield value about 85% during reaction time, with low mean values of CH₄ and CO selectivities of 3.4% and 11%, respectively and a low carbon formation. The better performance of y= 0.1 catalyst could be attributed to the minor proportion of segregated phases, thus a controlled expulsion of Ni is successfully reached.     

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。     

Ni-Fe/蒙脱土催化剂催化乙醇水蒸气重整制氢的研究

采用浸渍法制备了一系列Ni-Fe/蒙脱土(MMT)催化剂,并应用于乙醇水蒸气重整制氢反应(ESR)。采用X射线衍射(XRD)、N_2吸附脱附分析和H_2-程序升温还原(H_2-TPR)表征手段对催化剂的物理化学性质、还原性能、碳沉积等进行了研究。结果表明,Ni-Fe/MMT催化剂中,Ni、Fe高度分散在载体MMT层间及表面,而且Fe的加入降低了Ni颗粒的粒径,增强了Ni~(2+)与载体的相互作用力。以10Ni5Fe/MMT为催化剂,在反应温度为500℃、水醇比为3∶1、空速为12 h~(-1),反应进行30 h后,乙醇转化率为100%,氢气选择性仍保持72%,副产物CO和CH_4含量明显降低。这是因为催化助剂Fe的引入,一方面,提高了Ni的分散度,使得ESR低温活性较好;另一方面,减小了Ni颗粒粒径,小颗粒的Ni有利于抑制甲烷的生成,并且Fe的加入加强了甲烷重整和水煤气变换反应,提高产物中氢气的选择性。     

催化剂Ni/Y2O3上低温乙醇水蒸气重整制氢研究——氢气预还原对催化剂性能的影响

用浸渍－热分解－氢还原法(IHDHR)和浸渍－热分解法(IHD)分别制备了两种纳米尺寸的Ni/Y2O3催化剂，并应用X-光电子能谱、X-射线衍射、BET比表面测试等分析技术对两种催化剂的结构进行了表征和比较。采用固定床反应器对两种催化剂的催化性能进行实验测试。结果表明，氢气预还原与否对该纳米Ni/Y2O3催化剂的催化性能有一定的影响，经过氢气预还原的催化剂对低温乙醇水蒸气重整反应表现出较高的活性和稳定性，250?℃时，乙醇的转化率达到81.9%；320 ℃时，乙醇的转化率达到95.3%，对氢气的选择性为53.6%。对经过氢预还原的Ni/Y2O3催化剂进行了60 h的稳定性测试。     

镍负载量对乙醇水蒸气重整制氢催化性能和催化剂的影响

采用稳态实验对镍负载量对Ni/MgO催化剂在乙醇水蒸气重整反应的影响进行了研究。结果表明,在101.3kPa下,镍负载量越高,催化剂的活性越高。对于催化剂的选择性,存在一个最佳镍负载量为10%Ni/MgO。按选择性从大到小排序,不同镍负载量的催化剂为：10Ni/MgO>15Ni/MgO>12.5Ni/MgO>7.5Ni/MgO≈5Ni/MgO。热分析表明,焙烧过程中不同镍负载量的催化剂镍前体与载体前体之间发生的相互作用不同。XRD和TPR 表征结果显示,催化剂的晶体结构和还原特性也与催化剂上镍的负载量有关。焙烧过程中样品10Ni/MgO上镍前体与载体前体发生了两种相互作用, 并且其氧化态与其他催化剂相比具有特殊的结构和还原性。说明催化剂的选择性不仅受活性相Ni的影响而且受Ni活性相周围环境的影响。     

Ce改性Co/SEP催化剂对乙醇重整制氢的影响

采用海泡石（SEP）为载体,通过化学沉淀法制备了Co/SEP和Co-Ce/SEP催化剂,对催化剂进行X射线衍射（XRD）、H₂-程序升温还原（H₂-TPR）和透射电镜（TEM）等表征。结果表明,Ce的加入显著改善催化剂的分散度和还原性;两种催化剂应用于乙醇重整制氢实验,考察Ce的加入、反应时间、反应温度和水碳比（S/C比）对制氢的影响。结果表明,在WHSV为20.5h^-1,水碳比（S/C）为3,反应温度600℃时,Co-Ce/SEP乙醇转化率和氢气产率达到最高,分别为85%和65%。同时Ce的添加能使Co-Ce/SEP拥有更优的活性和稳定性。     

负载Ni催化剂上低温甘油蒸汽重整制氢

采用等体积浸渍法制备了Al₂O₃、CeO₂、TiO₂及MgO负载Ni催化剂,考察了它们对甘油蒸汽重整制氢反应的催化性能。采用X射线衍射、N₂吸附、透射电镜及H₂程序升温还原等方法对催化剂进行了表征。结果表明,载体对Ni催化剂的活性有显著影响。在400 ℃下Ni/CeO₂的催化活性明显好于其他催化剂,活性次序为Ni/CeO₂> Ni/Al₂O₃ > Ni/TiO₂ ~ Ni/MgO。Ni/CeO₂也具有好的稳定性,反应20 h未见活性下降,甘油转化率70%,氢气收率69.2%。这与CeO₂的本性及其与活性组分的相互作用有关。Al₂O₃具有较大的比表面积与孔体积,有利于CO吸附及甲烷化反应的进行,使得Ni/Al₂O₃催化剂在较高温度下具有很高的甘油转化率85.7%,但H₂选择性较差。由于MgO载体与活性组分强的相互作用而生成NiMgO₂固溶体,导致Ni/MgO低温活性差。     

Effect of crystallite size on the catalysis of alumina-supported cobalt catalyst for steam reforming of ethanol

The selectivity for steam reforming of ethanol on alumina-supported cobalt catalysts is closely related to the crystallite size of cobalt, which varies the strength of ethanol adsorption.     

负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究

采用等体积浸渍法和共沉淀法制备了Ni催化剂,在固定床反应器上考察了Ni负载量、焙烧温度、反应温度等因素对乙二醇低温重整制氢反应活性和选择性的影响。应用X射线衍射、氮物理吸附、H₂程序升温还原等技术对负载型Ni催化剂进行了表征。结果表明,共沉淀法制备的Ni/CeO₂催化剂具有较小的NiO颗粒与CeO₂载体颗粒粒径,催化活性较高。添加少量氧化钴到Ni/CeO₂催化剂中可使H₂收率达72.6%,EG转化率达93.1%。在CeO₂中添加Al₂O₃能提高负载Ni催化剂的活性,乙二醇转化率达94.0%,H₂收率达67.0%;但添加SiO₂则使其活性明显变差。     

Low CO content hydrogen production from oxidative steam reforming of ethanol over CuO-CeO2 catalysts at low-temperature

CuO-CeO₂ catalysts were prepared by a urea precipitation method for the oxidative steam reforming of ethanol at low-temperature. The catalytic performance was evaluated and the catalysts were characterized by inductively coupled plasma atomic emission spectroscopy, X-ray diffraction, temperature-programmed reduction, field emission scanning electron microscopy and thermo-gravimetric analysis. Over CuO-CeO₂ catalysts, H₂ with low CO content was produced in the whole tested temperature range of 250–450 °C. The non-noble metal catalyst 20CuCe showed higher H₂ production rate than 1%/oRh/CeO₂ catalyst at 300–400 °C and the advantage was more obvious after 20 h testing at 400 °C. These results further confirmed that CuO-CeO₂ catalysts may be suitable candidates for low temperature hydrogen production from ethanol.     

Reinforced nickel catalysts for steam reforming of methane to synthesis gas

XRD, mercury porosimetry, low-temperature nitrogen adsorption and electron microscopy were used to study peculiarities of the formation of reinforced composite nickel catalysts. The catalysts were prepared by sintering powdered metallic nickel with a supported nickel catalyst (GIAP-3 or NIAP-18) applied to a reinforcing stainless steel gauze. It was found that a metal matrix, in the pores of which supported catalyst particles were distributed, was formed in the composite catalysts. The NIAP-18-based catalyst exceeded the GIAP-3-based catalyst in activity toward the methane steam reforming. The NIAP-18-based catalyst was as active as the Cr₂O₃-doped NIAP-18-based catalyst, but showed a worse coke-resistance. A chromium oxide additive increased the activity of the GIAP-3-based catalyst.     

湿混法制备甲醇氧化重整制氢CuZnAlZr催化剂

用简易湿混法制备了用于甲醇氧化重整制氢的CuZnAlZr催化剂,与共沉淀法制备的催化剂比较,结果表明,湿混法制备的催化剂具有相当的中高温活性和略低的低温活性,有较高的CO2选择性。XRD、TPR、TG-DSC等表征结果显示,湿混法制备的催化剂中铜组分易于向表面迁移和富集,并可能与氧化铝作用生成铜铝复合氧化物,具有了更高的Cu分散度和Cu0比表面浓度。湿混法制备的催化剂对甲醇氧化重整反应有较好的稳定性,经100 h的连续反应,在275 ℃时甲醇转化率在90％以上,重整气中氢气体积分数大于60％,CO2选择性接近99％。     

Kinetics of methane steam reforming on a Ni on alumina-titania catalyst

The kinetics of methane steam reforming on a nickel on alumina-titania catalyst, was studied in the range of 773–873 K. A Hougen-Watson type model gives good agreement with the experimental rates.     

Cu/Ni负载型Beta分子筛催化剂的乙醇水蒸气重整制氢催化性能研究

采用等体积浸渍的方式,在全硅Beta分子筛载体上担载Cu、Ni活性组分,制备出一系列xCuyNi-ABZ多功能乙醇水蒸气重整制氢催化剂。通过XRD、TEM、SEM-EDX以及XPS等多种表征手段,研究催化剂的结构特性、活性组分含量等因素对催化性能的影响,依据反应产物分布,揭示其作用机理。结果表明,以Beta分子筛为载体可促使活性组分以纳米颗粒的形式高度分散于载体表面,并且存在较强的载体-金属作用力。与传统SiO_2为载体催化剂相比,2.5Cu2.5Ni-ABZ催化剂具备良好的乙醇水蒸气重整催化性能,当反应温度为450℃,实现100%的乙醇转化率和67.23%的H_2选择性,且副产物CO(4.14%)、CH_4(5.65%)含量相对较低。这可归因于Cu和Ni活性组分间的高效协同作用,Cu具有良好的乙醇脱氢性能,生成反应中间体乙醛;在反应过程中,乙醛的重整和分解是两个受温度影响的竞争反应,Ni组分利用其较强的C-C键断裂能力,随温度的升高,乙醛重整反应占主导作用,生成目标产物H_2。通过对反应后样品分析表明,2.5Cu2.5Ni-ABZ催化剂具备良好的抗烧结和抗积炭催化性能。     

Hydrogen generation from steam reforming of ethanol in dielectric barrier discharge

Dielectric barrier discharge (DBD) was used for the generation of hydrogen from ethanol reforming. Effects of reaction conditions, such as vaporization temperature, ethanol flow rate, water/ethanol ratio, and addition of oxygen, on the ethanol conversion and hydrogen yield, were studied. The results showed that the increase of ethanol flow rate decreased ethanol conversion and hydrogen yield, and high water/ethanol ratio and addition of oxygen were advantageous. Ethanol conversion and hydrogen yield increased with the vaporization room temperature up to the maximum at first, and then decreased slightly. The maximum hydrogen yield of 31.8% was obtained at an ethanol conversion of 88.4% under the optimum operation conditions of vaporization room temperature of 120 ?C, ethanol flux of 0.18 mL/min, water/ethanol ratio of 7.7 and oxygen volume concentration of 13.3%.     

Improved catalytic performance of Ni catalysts for steam methane reforming in a micro-channel reactor

Milliseconds process to produce hydrogen by steam methane reforming （SMR） reaction, based on Ni catalyst rather than noble catalyst such as Pd, Rh or Ru, in micro-channel reactors has been paid more and more attentions in recent years. This work aimed to further improve the catalytic performance of nickel-based catalyst by the introduction of additives, i.e., MgO and FeO, prepared by impregnation method on the micro-channels made of metal-ceramic complex substrate. The prepared catalysts were tested in the same micro-channel reactor by switching the catalyst plates. The results showed that among the tested catalysts Ni-Mg catalyst had the highest activity, especially under harsh conditions, i.e., at high space velocity and/or low reaction temperature. Moreover, the catalyst activity and selectivity were stable during the 12 h on stream test even when the ratio of steam to carbon （SIC） was as low as 1.0. The addition of MgO promoted the active Ni species to have a good dispersion on the substrate, leading to a better catalytic performance for SMR reaction.     

甲醇水蒸气重整制氢Pd/ZnO催化剂的研究

采用并流共沉淀法制备Pd／ZnO甲醇水蒸气重整制氢催化剂,考察了Pd的质量分数和还原温度对催化剂性能的影响。结果表明,当Pd质量分数为15．9％,还原温度为573K时,催化剂有较好的甲醇转化率及二氧化碳选择性。TPR结果表明,PdO在室温下被还原为金属Pd,在440K开始有部分ZnO被还原。XRD分析结果表明,PdZn合金是甲醇水蒸气重整反应的活性中心;在21．9％Pd／ZnO催化剂上出现了Pd2Zn合金相,导致催化剂的活性下降;反应过程中还原催化剂形成PdZn合金,其活性不如相同条件下纯氢还原的。15．9％Pd／ZnO催化剂及工业铜基催化剂的初始稳定性结果显示,在8h内,15．9％Pd／ZnO催化剂上甲醇转化率保持在66％以上,而铜基催化剂的活性下降了14．4％。     

有机蒙脱土负载镍催化剂上乙醇重整制氢

采用浸渍法制备了有机改性蒙脱土(OMt)负载的Ni/有机蒙脱土(Ni/OMt)催化剂,用于乙醇重整制氢;通过XRD、FT-IR、H₂-TPR、SEM、XPS和氮吸附等手段对催化剂进行了表征分析。结果表明,与未改性的蒙脱土负载的Ni催化剂(Ni/MMT)相比,有机改性可显著提高其比表面积、孔容和金属Ni的分散度,降低碳沉积量,改善Ni/MMT催化剂的稳定性。Ni/OMt催化剂表现出较高的乙醇重整制氢催化性能,在773K下反应30 h,乙醇转化率保持在100%,氢气选择性为70%;而Ni/MMT催化剂在反应10 h即开始失活,碳沉积严重,同时产生副产物乙烯和乙醛。使用十六烷基三甲基溴化铵(CTAB)改性可促进Ni高分散在MMT层板上,抑制积炭对活性金属Ni包裹,提高其乙醇重整氢气选择性、降低乙烯和乙醛的选择性。     

花状微球NiO/CeO_2催化剂上乙醇水蒸气重整制氢研究

用水热法制备微米尺寸CeO2花状微球粉体,并通过浸渍/热分解法在该粉体上担载纳米尺寸的NiO颗粒,制得催化剂NiO/CeO2。对催化剂进行了XRD、SEM、XES和BET物性表征。经固定床反应器对催化剂的催化性能进行测试。装载1.0 g催化剂,液体处理量0.05 mL/min。结果表明,该方法合成的催化剂NiO/CeO2对低温乙醇水蒸气重整反应表现出较高的活性和稳定性。同时通过微量Cr、Zn、Cu的加入在低温区抑制了CO、CH4的生成,提高了H2的产率和催化剂的抗积炭能力。该催化剂连续稳定性测试达到2 000 h;进行反复起动稳定性测试12次后,未表现出失活特征。     

吸收增强式甲烷水蒸气重整制氢循环反应模拟

吸收增强式甲烷水蒸气重整制氢反应可以生成高浓度的H2和较低浓度的CO、CO2。研究建立了考虑钙基吸收剂活性下降对吸收增强式甲烷水蒸气重整制氢过程影响的多次循环反应模型,在实验数据验证的基础上,计算了三种吸收剂活性下降特性对吸收增强式重整制氢过程的影响。结果表明,对于石灰石吸收剂,产生高纯H2的时间随循环次数的增加而急剧下降;白云石循环反应活性提高,产生高纯H2的时间随循环次数的增加而缓慢下降;CaO/Ca12Al14O33的循环使用次数明显大于石灰石和白云石。