微通道内甲烷/湿空气重整转化效率实验研究

用沉淀法制备了涂覆在微通道内壁面的Ni/Al2O3催化剂,在自行搭建的实验系统上进行了微通道内甲烷/湿空气催化重整的实验研究,考察了催化壁面温度、空碳比及甲烷体积流量对甲烷/湿空气重整转化效率的影响,并与数值计算结果进行对比.结果表明,随着催化温度的升高,甲烷转化率不断升高;相同水碳比下,甲烷的催化转化率随着空碳比的增大而增大;随着甲烷体积流量的增大,甲烷转化效率呈现先增大后减小的变化规律.反应温度为1 023 K,甲烷体积流量为20 mL/min时,实验所得甲烷转化率达到最大值,为61.3％.     

Ni-Rh/Al2O3催化剂上甲烷-氘化氢间的氢氘交换性能

采用Ni-Rh/Al₂O₃催化剂,在固定床微型反应器上考察了Ni-Rh/Al₂O₃催化剂对甲烷的氢氘交换的催化性能。结果表明,在进料组成不变的条件下,当温度低于692K时,甲烷的转化率随温度的升高而快速升高,当温度高于692K时,甲烷的转化率不随温度的升高而变化;当温度低于692K时,甲烷的转化率随反应物流量的增加而明显减小,当温度高于692K时,甲烷的转化率基本不随温度和反应物流量的变化而变化;在反应物总流量不变的条件下,当HD/CH₄流量比为1.1～2.5时,甲烷的转化率随着HD/CH₄流量比增加而减小。     

Ni-Mn/Al_2O_3催化剂在浆态床中CO甲烷化催化性能

采用共浸渍法制备了Ni-Mn/Al2O3催化剂,考察了助剂Mn的含量对催化剂结构及浆态床CO甲烷化性能的影响。采用XRD、H2-TPR、BET、TEM、H2-化学吸附等表征对催化剂进行了测试分析,结果表明,Mn助剂的引入能够促进Ni物种在载体表面的分散,减弱Ni物种与载体的相互作用,降低催化剂的还原温度,提高催化剂的比表面积,减小活性金属Ni的晶粒尺寸。随着Mn含量的增加,Ni-Mn/Al2O3催化剂的甲烷化性能先升后降,其中以Mn含量为4%(质量分数)时的催化甲烷化性能最佳,添加过量的Mn导致活性组分Ni被部分覆盖,催化甲烷化性能下降。通过对16Ni4Mn/Al2O3催化剂样品的浆态床反应温度及反应压力的研究发现,当反应温度为280℃、反应压力为1.5 MPa时,催化剂样品16Ni4Mn/Al2O3的CO转化率及CH4选择性分别达到96.2%和88.8%。     

MgO/La2O2CO3催化剂上的低温甲烷氧化偶联

共沉淀法制备的MgO/La2O2CO3催化剂使甲烷氧化偶联(OCM)在炉温460℃时开始反应,且使反应在50℃炉温下至少24 h。助剂Ni的加入降低了起始和最低反应温度,使催化剂在380℃的炉温下开始反应,之后在无热源的情况下可使反应至少24 h。助剂Zn的加入提高了反应活性,使C2的选择性提高了6%,但同时对低温反应不利,反应在炉温100℃下6 h后自动停止。OCM体系中的强放热反应为OCM温和反应提供了热源。催化剂中的La2O2CO3是维持低温甲烷氧化偶联反应的关键H活性组分。     

La_2O_3含量对La-Ni/ZrO_2-Al_2O_3催化剂甲烷化性能的影响

采用浸渍法制备了复合氧化物ZrO_2-Al_2O_3,在此基础上采用共浸渍法制备了La-Ni/ZrO_2-Al_2O_3催化剂,考察了催化剂中La2O3含量对催化剂CO甲烷化活性的影响,并利用BET、XRD和TPR对催化剂的物化性能进行了分析。结果表明当La2O3含量为2%~6%(质量分数,下同)时,其在低温和高温时的催化活性均比Ni/ZrO_2-Al_2O_3有一定的提升。另外比较了催化剂4La-Ni/ZrO_2-Al_2O_3和Ni/ZrO_2-Al_2O_3在500℃下连续反应100 h的活性和积碳,结果显示催化剂4La-Ni/ZrO_2-Al_2O_3具有很好的稳定性和优良的抗积碳性能。     

不同工艺条件下耐硫甲烷化催化剂的反应活性研究

考察了钼基耐硫甲烷化催化剂在不同反应温度下的催化活性,结果表明反应温度在560℃附近时甲烷化活性最高。在此温度下研究了空速、原料气中H2S、H2O、CO2、CH4、H2/CO等浓度对反应活性的影响,结果表明,原料气中H2S含量的增加有利于提高催化剂的甲烷化反应活性;H2O的加入促进了水煤气变换反应的进行但抑制了甲烷化反应,因此CO转化率虽没有下降但甲烷化效率却有所降低;添加CH4对甲烷化反应没有明显影响,而添加CO2则明显抑制了甲烷的生成。结合催化剂表征结果进一步对各因素的影响机理进行了分析,这为耐硫甲烷化工艺条件优化及催化剂设计提供了重要依据。     

CH_4/CO_2重整反应中Ni-Co双金属催化剂的研究进展

从实验和理论两个方面介绍了CH_4/CO_2重整反应中可能影响高活性抗积碳的Ni-Co双金属催化剂的因素。在实验方面,催化剂的制备方法,催化剂中每一种金属的含量、煅烧温度、还原气氛以及反应条件等因素都可能影响催化剂的性能。在理论计算方面,介绍了四种Ni-Co催化剂模型,分别是只包括活性组分的均相模型和表面偏聚模型,以及包含有载体的Ni-Co/Mg O和Ni-Co/Al_2O_3模型。只包含活性组分的均相模型上CH_4解离以及C和O的反应都会造成积碳;表面偏聚模型上C和O的反应能够消除积碳。可见表面偏聚模型更适合作为CH_4/CO_2重整反应的催化剂模型。而在包含载体的模型上只研究了CO_2的吸附。通过对文献的总结,希望理论和实践相结合,为重整反应催化剂的制备提供指导。     

Pt的加入提高了PdO/Al2O3催化剂反应活性

采用共沉淀法同时制备了PdO/M-Al2O3（M=Ce、Zr、Ce-Zr）和PtO-PdO/M-Al2O3催化剂。考察了Pt的加入对PdO/M-Al2O3催化剂的影响,助剂Ce、Zr改性的PtO-PdO/Al2O3催化剂的甲烷催化燃烧反应性能以及催化剂预处理对催化反应性能的影响。结果表明,PtO-PdO/Ce-Al2O3催化剂的活性最好,其甲烷完全转化温度为475℃,比PdO/Ce-Al2O3催化剂低90℃。另外,用蒸馏水反复洗涤的催化剂相比于未经蒸馏水洗涤的催化剂具有较低的甲烷起燃温度和完全转化温度。     

甲烷化催化剂及反应机理的研究进展

概述了甲烷化反应在工业生产中的应用,重点介绍了甲烷化催化剂中活性组分、载体、助剂的种类及催化剂制备方法、条件对其催化性能的影响;分析了甲烷化催化剂失活的原因及甲烷化反应的机理,指出床层飞温和积碳是造成催化剂失活的主要因素,必须从甲烷化催化剂和工艺技术两方面予以改进;并对甲烷化催化剂研究进行了展望,提出高比表面复合载体的...     

MgO对Ni/Al_2O_3催化剂CO甲烷化性能的影响

采用浸渍法制备了添加MgO助剂的Ni/Al2O3催化剂,并用固定床微反装置考察了催化剂在CO甲烷化反应中的催化性能。利用N2物理吸附、X射线衍射、H2程序升温还原、H2脉冲化学吸附和热重等手段对催化剂的结构进行了表征。通过分析样品的还原特性发现,活性组分Ni与Al2O3间的强相互作用会导致催化剂上Ni物种较难还原。MgO的引入可以明显削弱Ni与载体间的强相互作用,提高催化剂的还原度,增加催化剂活性位的数目,同时MgO的存在还能促进Ni颗粒的分散,提高催化剂的抗积碳性能,进而提高催化剂的甲烷化活性。     

Online BET analysis of single-wall carbon nanotube growth and its effect on catalyst reactivation

A system combining pulse chemical vapor deposition (CVD) reaction and cryogenic gas sorption (BET) measurement capabilities was designed to allow the sequential synthesis and online analysis of single-wall carbon nanotubes (SWNTs). Cooling treatment in liquid nitrogen (77 K) during BET measurement was found to be efficient for restoring catalysts when deactivation occurs after carbon deposition. By this treatment, the methane conversion could be enhanced by up to seven times, such as from 5.8% to 42.6% mol. When the temperature changes from 850 °C to 77 K, the metal particles on the tip of nanotubes might contract and be separated from the graphite layer of the nanotubes, leading to more active sites on metal particles being exposed. The single point BET analysis of SWNT has been tested as an efficient method for the rapid online analysis of SWNTs produced by CVD.     

Open-air carbon coatings on fused quartz by laser-induced chemical vapor deposition

Carbon films are deposited on fused quartz substrates by CO₂ laser-induced chemical vapor deposition (LCVD) using a novel open-air coating system. The hydrocarbon precursor gases are methane, propane and butane. The deposition rates of the three hydrocarbon gases are determined by measuring the mass of the carbon film deposited at constant temperature, and validated by film thickness measurements obtained using an environmental scanning electron microscope. The results indicate that butane and propane have significant deposition at 1375-1500 K, while deposition starts at 1550 K for methane. All three hydrocarbons have an exponential increase in deposition rate. Deposition rates obtained with butane and propane show a much stronger influence of temperature compared to methane. Raman spectra of deposited carbon films indicate that the surface consists of glass-like or nanocrystalline carbon. The ratio of D-peak to G-peak Raman band intensities decreases as the deposition temperature is increased, which is possibly due to self-annealing and additional surface reaction during high temperature deposition. This finding indicates that the carbon film exhibits higher structural order at high deposition temperatures, which can significantly enhance the film’s hermeticity and mechanical properties for use as an optical fiber coating.     

Analysis of products of high-temperature pyrolysis of various hydrocarbons

Ethane, ethylene, acetylene, propane and neopentane have been pyrolyzed at 1173 K, and methane at 1372 K in a flow system, and the volatile pyrolysis products analyzed. Eleven aromatic hydrocarbons, containing 14 or fewer carbon atoms, accounted for 98 + % of the liquid products recovered in each case. Benzene was the main product, followed by naphthalene. No compounds with branched chains or multiple substituents were present, and compounds containing even numbers of carbons comprised 93–99% of each mixture. Acetylene was a major component of the gaseous effluent from each of the initial hydrocarbons. The effect of temperature on the composition of the gaseous effluent during pyrolysis of methane, ethane and ethylene was determined. Carbon film deposition from methane commenced at about 1273 K; from ethane at 1015 K and from ethylene at 1100 K, in each instance coinciding with the appearance of acetylene in the effluent. As the temperature was raised, at first the increase in the rate of carbon deposition closely followed the increase in the concentration of acetylene in the effluent. It is proposed that acetylene may be a common factor in the pyrolysis of aliphatic hydrocarbons, perhaps acting as the precursor of both surface carbon and aromatic hydrocarbons by a process of head-to-tail linkage of two-carbon units at active surface sites to form chains that then undergo dehydrogenation to carbon or cyclization and desorption as aromatic species.     

Cd改性拉长石催化甲烷裂解制C2烃

以Cd改性拉长石(Cd/Lab)为甲烷裂解催化剂制C2烃,通过XRD、XPS、TEM及GC对催化剂的结构、形貌和催化性能进行了表征与测试。利用固定床反应装置考察了金属掺杂量、反应温度、原料气空速等因素对拉长石催化甲烷裂解制C_2烃的影响。结果表明,当原料气空速为1 L/h、反应温度1073 K时,天然拉长石和Cd质量分数为1.0%的Cd改性拉长石催化甲烷裂解的转化率分别为3.32%和6.41%,且C_2烃的选择性99%。XRD、XPS、TEM等表征和催化性能结果表明,Cd2+进入到拉长石的碱金属位点,证明拉长石催化甲烷裂解的有效活性位点是碱金属位点。     

Mechanism of coke deposition on the surface of molybdenite

The formation of coke is studied by SEM/TEM on the basal plane of a thin (ca. 500 Å) single-crystal film of MoS₂. From exposure to benzene at 550 and 700 °C, which is exothermic in decomposition, carbon islands are formed on the face opposite to the exposure face; whereas for the endothermic decomposition of methane (at 700 °C), carbon islands are formed on the exposure face. This result provides a direct evidence for the carbon diffusion mechanism for coke deposition in which a temperature gradient is the driving force for carbon diffusion. It is demonstrated that the formation and growth of thin (perhaps monolayer) carbon islands can be studied by gold decoration/TEM. A gold-decoration/TEM study of coke formation of benzene on MoS₂ show that screw dislocations are not preferred sites for carbon deposition, and that steps on the basal plane are likely the active sites for decomposition of benzene.     

固体氧化物燃料电池Cu/Ni-LSCM阳极中n(Cu)/n(Ni)对碳沉积影响数值模拟研究

固体氧化物燃料电池(SOFC)使用碳氢化合物为燃料时,多孔阳极易出现严重的积碳的现象,导致阳极催化活性降低,电池功率密度下降以及电池寿命急剧衰减。铬酸镧基钙钛矿材料在高温氧化和还原气氛下具有较好的稳定性、电催化活性和抗积碳性能。建立LSCM以及Cu/Ni-LSCM中CH₄与CO₂干重整动力学模型,模型耦合了动量传递、质量传递、化学反应动力学、域微分方程以及气体在多孔介质中的传质模型,并利用该模型研究了Cu/Ni-LSCM阳极材料的抗积碳性能、催化活性以及孔隙率随时间的变化情况。得出结论:Cu的引入可以明显降低碳沉积速率,在一定基础上增加燃料转化率。其中CH₄热分解是形成积碳的主要原因。与此同时,模拟结果显示阳极燃料入口处为碳沉积最为严重的区域。     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

Adsorption of methane on corn cobs based activated carbon

Activated carbon was prepared with corn cobs and potassium hydroxide under optimized variables. Due to their botanical origin, corn cobs can be an excellent starting material to produce nanoporous carbon for natural gas storage. Samples with different BET surface areas were chosen to perform methane adsorption experiments. Methane adsorptions on corn cob based activated carbon were studied at four different pressures (500, 1000, 1500 and 2000 psi) and two different temperatures (298 K and 323 K) in a volumetric adsorption apparatus. The volume based methane adsorption results specified an ‘increase in the methane adsorption capacities of activated carbon with increasing surface area and showed that adsorption capacity of methane depends on pressure and temperature. The highest methane storage capacity was found to be 160 (v/v) at 298 K and 1500 psi. The applications include use in the transportation of natural gas, natural gas based vehicles, and adsorption of gas from landfills.     

Catalytic decomposition of methane over a wood char concurrently activated by a pyrolysis gas

The catalytic activity of a wood char towards CH₄ decomposition in a pyrolysis gas was investigated in a fixed bed reactor for maximising hydrogen production from biomass gasification. Wood char is suggested to be the cheapest and greenest catalyst for CH₄ conversion as it is directly produced in the pyrolysis facility. The conversion of methane reaches 70% for a contact time of 120 ms at 1000 °C. Because steam and CO₂ are simultaneously present in the pyrolysis gas, the carbon catalyst is continuously regenerated. Hence the conversion of methane quickly stabilises. Such a phenomenon is shown to be possible through the oxidation of the char by CO₂ and H₂O at high temperature, which prevents the blocking of the mouth of pores by the concurrent pyrolytic carbon deposition. In the experimental conditions, oxygenated functional surface groups are continuously formed (by steam and CO₂ oxidation) and thermally decomposed. The active sites for CH₄ chemisorption and decomposition are suggested to be the unsaturated carbon atoms generated by the evolution of the oxygenated functions at high temperature.     

The influence of calcination temperature on catalytic activities in a Co based catalyst for CO2 dry reforming

The carbon dioxide dry reforming of methane (CDR) reaction could be thermodynamically favored in the range of 800 to 1,000 °C. However, the catalyst in this reaction should be avoided at the calcination temperature over 800 °C since strong metal support interaction (SMSI) in this temperature range can decrease activity due to loss of active sites. Therefore, we focused on optimizing the temperature of pretreatment and a comparison of surface characterization results for CDR. Results related to metal sintering over support, re-dispersion by changing of particle size of metal-support, and strong metal support interaction were observed and confirmed in this work. In our conclusion, optimum calcination temperature for a preparation of catalyst was proposed that 400 °C showed a higher and more stable catalytic activity without changing of support characteristics.