Production of COX Free Hydrogen by Catalytic Decomposition of Methane Over Ni/HY Catalysts

In this present paper, we report catalytic decomposition of methane over Ni/HY catalysts, with varying Ni loading at 550 °C and atmospheric pressure. The relationships between catalyst performance and characterization of the fresh and used form of catalysts are discussed from the data obtained by scanning electron microscopy, X-ray diffraction analysis, temperature programmed reduction, O₂ pulse chemisorption and carbon elemental analyses. It is observed that, the catalytic activity of Ni/HY catalysts is high at initial stages and gradually decreased with time and finally deactivated completely. The yield of hydrogen and carbon nanofibers is strongly dependent on Ni loading. It is found that 20 wt% Ni/HY catalyst showed higher hydrogen yield over the other loadings.     

Study of Methane Decomposition on Fe/MgO-Based Catalyst Modified by Ni,Co, and Mn Additives

Catalytic decomposition of methane (CDM) generates clean hydrogen and carbon nanomaterials. In this study, methane decomposition to hydrogen and carbon was investigated over Ni-, Co-, or Mn-doped Fe/MgO catalysts. The doping effect of different metals, varying from 3 to 10?wt%, was investigated. The catalytic performance of the obtained materials (noted 15%Fe+x%metal/MgO) revealed that the doping effect of Ni, Co, and Mn significantly improved the activity of Fe/MgO. Among the Ni-doped catalyst series, the 15%Fe+3%Ni/MgO catalyst performed better than the rest of the Ni catalysts. The 6%Co-containing catalyst remained the best in terms of activity in the Co-doped catalyst series and the 15%Fe+6%Mn/MgO solid showed better methane conversion for the Mn-doped series. Overall, 3%Ni-containing catalyst displayed the best catalytic performance among all Ni-, Co-, and Mn-doped catalysts. XRD, N₂ sorption, and H₂ temperature-programmed reduction (TPR), Laser–Raman spectroscopy, thermogravimetric analysis (TGA) under air, and temperature-programmed oxidation (TPO) were used for catalyst characterization. The results revealed that all the doped catalysts exhibited better metallic active site distribution than 15%Fe/MgO and proved that metal doping played a crucial role in catalytic performance.     

Catalytic Methane Decomposition to Hydrogen over a Surface‐Protected Core‐Shell Ni@SiO2 Catalyst

Methane decomposition is a promising method to obtain CO_x‐free hydrogen. The main difficulty of this process is that the produced carbon would deposit on the active phase of the catalyst, leading to catalyst deactivation. In this study, a core‐shell‐structured composite catalyst comprising highly active Ni nanoparticles (NP) as core and mesoporous silica as shell is introduced. The silica shells were synthesized by using cetyltrimethylammonium bromide as template and tetraethyl orthosilicate as precursor. Ni NP and Ni@SiO₂ were examined as catalysts for hydrogen production by methane decomposition at different temperatures and gas hourly space velocities. The results show that the core‐shell catalyst exhibited much better stability in methane decomposition than Ni NP without silica shell and a traditional supported catalyst.     

Hydrogen Production from Ethanol Steam Reforming Over Supported Cobalt Catalysts

Hydrogen production was carried out via ethanol steam reforming over supported cobalt catalysts. Wet incipient impregnation method was used to support cobalt on ZrO₂, CeO₂ and CeZrO₄ followed by pre-reduction with H₂ up to 677 °C to attain supported cobalt catalysts. It was found that the non-noble metal based 10 wt.% Co/CeZrO₄ is an efficient catalyst to achieve ethanol conversion of 100% and hydrogen yield of 82% (4.9 mol H₂/mol ethanol) at 450 °C, which is superior to 0.5 wt.% Rh/Al₂O₃. The pre-reduction process is required to activate supported cobalt catalysts for high H₂ yield of ethanol steam reforming. In addition, support effect is found significant for cobalt during ethanol steam reforming. 10% Co/CeO₂ gave high H₂ selectivity while suffered low conversion due to the poor thermal stability. In contrast to CeO₂, 10 wt.% Co/ZrO₂ achieved high conversion while suffered lower H₂ yield due to the production of methane. The synergistic effect of ZrO₂ and CeO₂ to promote high ethanol conversion while suppress methanation was observed when CeZrO₄ was used as a support for cobalt. This synergistic effect of CeZrO₄ support leads to a high hydrogen yield at low temperature for 10 wt.% Co/CeZrO₄ catalyst. Under the high weight hourly space velocity (WHSV) of ethanol (2.5 h⁻¹), the hydrogen yield over 10 wt.% Co/CeZrO₄ was found to gradually decrease to 70% of its initial value in 6 h possibly due to the coke formation on the catalyst.     

甘油水蒸汽重整制氢Ni、Co、Fe催化剂的研究

采用等体积浸渍法制备了催化剂,研究了Ni/Al2O3,Fe/Al2O3,CoMo/Al2O3和NiCo/Al2O3催化剂对甘油水蒸汽重整制氢反应的催化效果,对催化剂进行BET、TPR、XRD表征,以氢产率为实验指标对催化剂进行了评价。研究结果表明,CoMo/Al2O3催化剂在温度650℃氢产率6.02。NiCo/Al2O3催化剂在温度600℃、水醇比16、液空速0.12 h-1条件下的氢产率为6.08。催化剂活性次序为NiCo/Al2O3Co-Mo/Al2O3Ni/Al2O3Fe/Al2O3。     

Methane Pyrolysis for CO2-Free H2 Production: A Green Process to Overcome Renewable Energies Unsteadiness

The Carbon2Chem® project aims to convert exhaust gases from the steel industry into chemicals such as methanol to reduce CO₂ emissions. Here, H₂ is required for the conversion of CO₂ into methanol. Although much effort is put to produce H₂ from renewables, the use of fossil fuels, especially natural gas, seems to be fundamental in the short term. For this reason, the development of clean technologies for the processing of natural gas with a low environmental impact has become a topic of utmost importance. In this context, methane pyrolysis has received special attention to produce CO₂-free H₂.     

Bi-metallic catalysts of mesoporous Al2O3 supported on Fe,Ni and Mn for methane decomposition: Effect of activation temperature

Methane decomposition reaction has been studied at three different activation temperatures (500 °C, 800 °C and 950 °C) over mesoporous alumina supported Ni–Fe and Mn–Fe based bimetallic catalysts. On co-impregnation of Ni on Fe/Al₂O₃ the activity of the catalyst was retained even at the high activation temperature at 950 °C and up to 180 min. The Ni promotion enhanced the reducibility of Fe/Al₂O₃ oxides showing higher catalytic activity with a hydrogen yield of 69%. The reactivity of bimetallic Mn and Fe over Al₂O₃ catalyst decreased at 800 °C and 950 °C activation temperatures. Regeneration studies revealed that the catalyst could be effectively recycled up to 9 times. The addition of O₂ (1 ml, 2 ml, 4 ml) in the feed enhanced substantially CH₄ conversion, the yield of hydrogen and the stability of the catalyst.     

Nonoxidative Activation of Methane

Effective utilization of methane remains one of the long-standing problems in catalysis. Over the past several years, various routes, both direct and indirect, have been considered for the conversion of methane to value-added products such as higher hydrocarbons and oxygenates. This review will focus on the range of issues dealing with thermal and catalytic decomposition of methane that have been addressed in the last few years. Surface science studies (molecular beam methods and elevated-pressure reaction studies) involving methane activation on model catalyst systems are extensively reviewed. These studies have contributed significantly to our understanding of the fundamental dynamics of methane decomposition. Various aspects of the nonoxidative methane to higher hydrocarbon conversion processes such as high-temperature coupling and two-step low-temperature methane homologation have been discussed.

Decomposition of methane results in the production of CO_x-free hydrogen (which is of great interest to state-of-the-art low-temperature fuel cells) and various types of carbon (filamentous carbon, carbon black, diamond films, etc.) depending on the reaction conditions employed; these issues will be briefly addressed in this review.     

Sn改性Raney Ni催化分解N,N-二甲基甲酰胺的研究

为了研究Sn含量和还原温度对Sn-RaneyNi催化剂的物理化学结构和催化分解N,N-二甲基甲酰胺(DMF)活性的影响,利用沉淀法制备了一系列不同Sn含量的Sn-RaneyNi催化剂,采用N2物理吸附、X射线衍射(XRD)和氢气程序升温还原(H2-TPR)等方法对不同Sn含量和不同还原温度制得的Sn-RaneyNi催化剂的比表面积、物相组成和还原性能进行了表征。以N,N-二甲基甲酰胺(DMF)为模型化合物,对Sn-RaneyNi催化剂的催化分解活性进行了评价。XRD表征结果表明,n(Sn)/n(Ni)为0.1的催化剂分别在723K和823K下还原生成Ni3Sn4和Ni3Sn合金晶相;n(Sn)/n(Ni)为0.15的催化剂在723K下还原形成Ni3Sn2合金晶相。H2-TPR结果表明,Ni-Sn合金的形成削弱了Sn和Ni与氧的结合能,使得Sn和Ni的还原峰向低温移动。催化分解DMF实验结果表明,当n(Sn)/n(Ni)为0.1、还原温度为723K时,Sn修饰RaneyNi催化剂能够将高浓度DMF(5%(wt))完全分解(分解率达100%),氢气的选择性达到86.8%。     

Structure and Catalytic Performance of Mg‐SBA‐15‐Supported Nickel Catalysts for CO2 Reforming of Methane to Syngas

A series of Mg‐modified SBA‐15 mesoporous silicas with different MgO contents were successfully synthesized by a simple one‐pot synthesis method and further impregnated with Ni. The Mg‐modified SBA‐15 materials and supported Ni catalysts were characterized by N₂ physisorption (BET), X‐ray diffraction (XRD), temperature‐programmed desorption of CO₂ (CO₂‐TPD), temperature‐programmed H₂ reduction (H₂‐TPR), and temperature‐programmed hydrogenation (TPH) techniques and used for methane dry reforming with CO₂. CO₂‐TPD results proved that the addition of Mg increased the total amount of basic sites which was responsible for the enhanced catalytic activity over the Mg‐modified Ni catalyst. The excellent catalytic stability of Ni/8Mg‐SBA‐15 was ascribed to less coking and higher stability of the Ni particle size due to the introduction of Mg.     

The Production of Straight Carbon Microfibers by the Cracking of Methane over Co-SBA-15 Catalysts

Cobalt incorporated SBA-15 (Co-SBA-15) catalysts were prepared by using hydrothermal synthesis and over which very straight carbon microfibers were made by cracking CH₄. The influence of Co loading (from 0.5 to 3 wt%) in SBA-15 and cracking temperature on the methane conversion, structures and morphologies of the microfibers was investigated. The highest yield of microfibers was obtained at 800 °C over the 2 wt% Co loaded SBA-15 catalyst. After 16 h reaction, the carbon fibers almost stopped further growth. The diameter of the carbon microfibers could be roughly controlled by judiciously adjusting the Co concentration in SBA-15. The carbon microfiber’s growth followed a root-growth mechanism. XRD, HRTEM and Raman studies confirmed that the microfibers were graphitic. The microfiber grown over the 0.5 wt% cobalt loaded SBA-15 catalyst had a higher degree of graphitic structural order than that obtained over the 2 wt% cobalt loaded one.     

Financial and Ecological Evaluation of Hydrogen Production Processes on Large Scale

Hydrogen is widely seen as energy carrier of the future. Different technologies are under development to produce hydrogen at competitive cost but with significantly reduced carbon footprint. Two conventional technologies, namely, methane steam reforming and coal gasification, are compared based on product cost and carbon footprint with four new technologies, i.e., metal‐oxide cycle, water electrolysis, biomass gasification, and methane pyrolysis. To evaluate the carbon footprint for methane pyrolysis, system extension and differential methods are applied. For the boundary conditions selected here, methane pyrolysis yields very good values for product cost and carbon footprint. Therefore, a cross industry technology development of methane pyrolysis was initiated.     

MgO改性CuZnAl催化剂上甲醇裂解制氢

为了提高甲醇裂解制氢的气体收率,减少液相副产物的生成量,采用共沉淀法制备MgO改性CuZnAl催化剂,通过BET、XRD、SEM、H_2-TPR、CO2-TPD对催化剂结构和物化性能进行表征分析,固定床中考察MgO改性CuZnAl催化剂对甲醇裂解制氢催化性能。结果表明,引入适量的MgO可提高催化剂比表面积和CuO的分散度,改善催化剂氧化还原性,提高催化剂活性和选择性。得到优化的催化剂CuZnAlMg_2,其组分质量比为m(CuO)∶m(ZnO)∶m(Al_2O_3)∶m(MgO)=16∶13∶3∶2。在反应温度280℃、反应压力1.0MPa和空速0.6h-1条件下,CuZnAlMg_2催化剂上甲醇裂解转化率为99.1%,气体收率为97.0%。对液相产物进行分析表明,加入适量MgO提高催化剂碱性,能有效抑制液相副产物生成,提高气体收率。     

Hydrogen Production from Ethanol Steam Reforming Over Ni/CeO2 Nanocomposite Catalysts

The organic polymer chitosan was used as the polymeric precursor for the synthesis of Ni/CeO₂ nanocomposite catalysts. The materials were characterized by N₂ physisorption, H₂ chemisorption, AA, XRD, TGA, TPR, SEM and TEM analyses. The catalysts provide very good reactivity in ethanol steam reforming compared to the conventional Ni/CeO₂ catalyst prepared by the impregnation method using a commercial support. High hydrogen selectivity (>75%) was obtained on Ni/CeO₂ catalysts by operating at a temperature range of 325–500 °C and a H₂O/C₂H₅OH molar ratio of 3. It was verified that the catalytic behavior could be influenced depending on the experimental conditions employed.     

Methane decomposition on Fe–Cu Raney-type catalysts

The decomposition of methane into hydrogen and carbon was studied on Fe–Cu catalysts of Raney-type. The activity of the catalysts was assessed by comparing the experimental conversions with the calculated equilibrium conversions for each set of experimental conditions. The stability of the catalysts was assessed by comparing the maximum conversions with the conversions at the end of 5-hour tests. The carbon deposits obtained consist mostly of carbon nanofibers. Good results were obtained when the Fe–Cu Raney-type systems were thermally treated in situ at 600 °C, as a result of incipient alloy formation. These catalysts showed higher stability than the monometallic Raney-Fe catalysts.     

Small Amounts of Rh-Promoted Ni Catalysts for Methane Reforming with CO2

Small amounts of Rh-promoted Ni/-Al₂O₃ catalysts possessed higher activity than pure Ni/-Al₂O₃, Rh-Al₂O₃ catalysts and exhibited excellent coke resistance ability in methane reforming with CO₂. XRD, H₂-TPR, CO₂-TPD and coking reaction (via CH₄ temperature-programmed decomposition) indicated that Rh improved the dispersion of Ni, retarded the sintering of Ni and increased the activation of CO₂ and CH₄ on the surface of catalyst.     

Preparation of Highly Active Nickel Catalysts Supported on Mesoporous Nanocrystalline γ‐Al2O3 for Methane Autothermal Reforming

Autothermal reforming (ATR) of methane was carried out over nanocrystalline Al₂O₃‐supported Ni catalysts with various Ni loadings. Mesoporous nanocrystalline γ‐Al₂O₃ powder with high specific surface area was prepared by the sol‐gel method and employed as support for the nickel catalysts. The prepared samples were characterized by X‐ray diffraction, Brunauer‐Emmett‐Teller, temperature‐programmed reduction, temperature‐programmed hydrogenation, and scanning electron microscopy techniques. It is demonstrated that the methane conversion increased with increasing in Ni content and that the catalyst with 25 wt % Ni exhibited the highest activity and a stable catalytic performance in the ATR process, with a low degree of carbon formation. Furthermore, the effects of the reaction temperature, the calcination temperature, the steam/CH₄ and O₂/CH₄ ratios, and the gas hourly space velocity on the catalytic performance of the 25 % Ni/Al₂O₃ catalyst were investigated.     

Carbon Dioxide Reforming of Methane Over Nanocomposite Ni/ZrO2 Catalysts

A systematic study of the size effect of zirconia nanocrystals on nickel-catalyzed reforming of methane with CO₂ shows that extremely stable Ni/ZrO₂ catalysts are obtainable by hydrogen reduction of impregnated nickel nitrate on zirconia particles with sizes less than 25 nm. The same preparation method with larger particles of zirconia results in catalyst samples that deactivate rapidly in the reforming reaction. Comprehensive characterization with XRD, TPR/TPD, and TEM shows that the stable Ni/ZrO₂ catalysts are better described as nanocomposites of size comparable to Ni metal (9-15 nm) and zirconia (7-25 nm) nanoparticles. The high percentage of the Ni-zirconia boundary or perimeter in the nanocomposite catalysts is believed to be crucial for the extremely stable catalytic activity.     

复合载体Ni催化剂乙醇水蒸气重整制氢研究

用沉积-沉淀法制备了以ZnO为主要组分的多种复合载体（ZnO-Al2O3、ZnO-TiO2、ZnO-MgO、ZnO-CeO2、ZnO-ZrO2）Ni基催化剂,在固定床反应器上考查了催化剂的乙醇水蒸气重整制氢反应性能。结果表明,催化剂复合载体组分对乙醇水蒸气重整制氢性能有影响,其中,在较低温度（400～470℃）Ni/ZnO催化剂的催化性能最优,而在较高温度（485～550℃）Ni/ZnO-TiO2催化剂有相对最优的催化性能。催化剂的XRD、SEM等表征表明,Ni催化剂活性组分分散良好,催化剂颗粒大小较为均匀,同时也观察到使用后的催化剂表面有积炭生成。