Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

Economic competitiveness of compact steam methane reforming technology for on-site hydrogen supply: A Foshan case study

On-site hydrogen production through steam-methane reforming (SMR) from city gas or natural gas is believed to be a cost-effective way for hydrogen-based infrastructure due to high cost of hydrogen transportation. In recent years, there have been a lot of on-site hydrogen fueling stations under design or construction in China. This study introduces current developments and technology prospects of skid-mounted SMR hydrogen generator. Also, technical solutions and economic analysis are discussed based on China's first on-site hydrogen fueling station project in Foshan. The cost of hydrogen product from skid-mounted SMR hydrogen generator is about 23 CNY/kg with 3.24 CNY/Nm³ natural gas. If hydrogen price is 60 CNY/kg, IRR of on-site hydrogen fueling station project reaches to 10.8%. While natural gas price fall to 2.3 CNY/Nm³, the hydrogen cost can be reduced to 18 CNY/kg, and IRR can be raised to 13.1%. The conclusion is that skid-mounted SMR technology has matured and is developing towards more compact and intelligent design, and will be a promising way for hydrogen fueling infrastructures in near future.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

Prediction of methane adsorption content in continental coal-bearing shale reservoir using SLD model

Shale gas, as an important unconventional resource, has drawn global attention. It is mainly composed of adsorption gas and free gas. Adsorption gas content could play an important guiding role on both the selection of favorable perspective area and the exploration and exploitation of shale gas resources. In order to accurately measure adsorption gas content, a new approach was established to predict the adsorption isotherm of methane on shale. Based on the simplified local-density (SLD) method, both the adsorption isotherms of illite, illite/smectite mixed-layer, cholorite and type III kerogen and the total shale rock could be well fitted. The fitting results show good coincidences with the true experimental test data, which proves the method is reasonable and dependable and the prediction results are effective and credible. In addition, the good simulation results show that the SLD parameters can reflect the pore structure characteristics and corresponding adsorption characteristics of the shale samples, which can be used for the quantitative characterization of shale pore system.     

Forging furnace with thermochemical waste-heat recuperation by natural gas reforming: Fuel saving and heat balance

This paper considers thermochemical recuperation (TCR) of waste-heat using natural gas reforming by steam and combustion products. Combustion products contain steam (H₂O), carbon dioxide (CO₂), and ballast nitrogen (N₂). Because endothermic chemical reactions take place, methane steam-dry reforming creates new synthetic fuel that contains valuable combustion components: hydrogen (H₂), carbon monoxide (CO), and unreformed methane (CH₄). There are several advantages to performing TCR in the industrial furnaces: high energy efficiency, high regeneration rate (rate of waste-heat recovery), and low emission of greenhouse gases (CO₂, NO_x). As will be shown, the use of TCR is significantly increasing the efficiency of industrial furnaces – it has been observed that TCR is capable of reducing fuel consumption by nearly 25%. Additionally, increased energy efficiency has a beneficial effect on the environment as it leads to a reduction in greenhouse gas emissions.     

含煤盆地深层“超饱和”煤层气形成条件

中国深层煤层气资源丰富，但总体勘探和认识程度较低，尚未形成较为系统的深层煤层气地质理论。通过解剖分析准噶尔盆地白家海凸起和鄂尔多斯盆地临兴区块深层"超饱和"煤层气井的试气/生产动态，估算原地游离气的含气量，分析了深层"超饱和"煤层气的形成条件。研究表明：①深层"超饱和"煤层气储层中除吸附气外，还含有原地游离气，用常规试气方法可直接获得气流，煤层气的产出不明显依赖于排水降压；②埋藏超过一定深度，在煤阶和温度的综合作用下，煤的吸附能力将随埋深的继续增加而降低，煤层中吸附气的饱和度有增加的趋势，在达到吸附饱和后，出现原地游离气并形成"超饱和"煤层气，盆地深层具有"超饱和"煤层气形成的优势条件；③由于地温梯度和压力梯度的不同，不同盆地"超饱和"煤层气出现的临界深度不同，异常高压和异常高热流可以降低深层"超饱和"煤层气形成的临界深度；④深层"超饱和"煤层气开发具有大大缩短见气时间、充分利用地层能量和累积产水量低等优势，有望成为未来煤层气勘探开发的一个重要领域。     

低剂量抑制剂Inhibex501存在下的甲烷水合物相平衡研究

含动力学抑制剂的天然气水合物相平衡研究对新型低剂量抑制剂的开发具有指导作用。在283.6 ~ 290.9 K和7.51 MPa ~ 15.97 MPa的温压范围内研究了抑制剂Inhibex501及其溶剂2-乙二醇单丁醚对甲烷水合物相平衡条件的影响。实验结果显示，0.5wt%和2.0wt%浓度的Inhibex501对甲烷水合物形成的热力学条件具有促进作用，能使甲烷水合物形成移向更高的温度或者更低的压力，而2-乙二醇单丁醚在浓度0.2wt% ~ 1.0wt%范围几乎不改变甲烷水合物形成的热力学条件，N-乙烯基己内酰胺与N-乙烯基吡咯烷酮的共聚物对水合物形成热力学条件的改变起主要作用。     

负载型复合载体及其镍基催化剂的性能

采用溶胶-凝胶法制备了负载型ZrO_2/Al_2O_3和ZrO_2/Al_2O_3-SiO_2复合载体,研究了不同复合载体对Ni基催化剂CO_2重整甲烷反应和性能的影响,并用XRD、IR、TPR、TPD和BET等方法对复合载体及催化剂进行了表征。结果表明,ZrO_2负载在基载体后比表面积、碱性、活性组分Ni的分散度和Ni与ZrO_2的相互作用增大。NiO在复合载体表面的分散容量与ZrO_2的负载量有关,ZrO_2的负载量为37．5%时NiO的分散容量达最高值(24．0%)。与Ni/ZrO_2相比,Ni/ZrO_2/Al_2O_3-SiO_2和Ni/ZrO_2/Al_2O_3催化剂对CO_2的吸附能力增大,CO_2吸附量增加,酸强度降低,CO_2重整CH_4反应活性提高,其中以Ni/ZrO_2/Al_2O_3催化剂的活性最好。     

溶胶-凝胶法制备Na_2WO_4~-Mn/SiO_2催化剂及其甲烷氧化偶联反应性能的研究

采用溶胶-凝胶法制备了一系列5%Na2WO4-2%Mn/SiO2催化剂;用XRD、XPS、BET、O2-TPD和CO2-TPD等方法对催化剂进行了表征,并考察了对甲烷氧化偶联反应的催化性能。结果表明,与常规浸渍法相比,采用溶胶-凝胶法制备的Na2WO4-Mn/SiO2催化剂中W和Mn的原子浓度在催化剂表面和体相分布较为接近,而且两种制备方法所得的催化剂具有相似的催化性能,Na2WO4与α-方石英之间的相互作用,催化剂释放晶格氧的能力,碱性强弱是影响甲烷氧化偶联活性的关键因素。