Rh/SiO_2催化剂上甲烷部分氧化制合成气的反应机理

采用原位Raman光谱技术,在原料气中的O2未完全耗尽的条件下,对CH4部分氧化制合成气反应的Rh/SiO2催化剂床层前部贵金属物种的化学态以及由CH4解离所生成的碳物种进行了表征.在此基础上采用脉冲反应和同位素示踪技术,比较了CH4的部分氧化及其与H2O和CO2的重整等反应对催化剂床层氧化区内CO和H2生成的相对贡献,并将实验结果与Ra-man光谱表征结果进行了关联.结果表明,在600°C下将还原后的4%Rh/SiO2催化剂切入CH4:O2:Ar=2:1:45原料气,催化剂床层前部未检测到铑氧化物的Raman谱峰,但可清晰检测到源于CH4解离的碳物种;在700°C和接触时间小于1ms的条件下,催化剂床层的氧化区内已有大量CO和H2生成,在相同的实验条件下,CH4与H2O或CO2重整反应对氧化区内合成气生成的贡献则很小;以CH4:16O2:H218O:He=2:1:2:95为原料气的同位素示踪实验结果表明,在原料气中16O2未完全耗尽的情况下,反应产物中C16O的含量占CO生成总量的92.3%,表明CO主要来自CH4的部分氧化反应.上述结果均表明,在O2存在下Rh/SiO2催化剂上CO和H2可以通过CH4直接解离和部分氧化机理生成.     

In-Situ FT-IR Investigation Methane to Syngas over of Partial Oxidation of Rh/SiO2 Catalyst

Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.     

甲烷催化部分氧化制合成气的反应机理

借助脉冲反应、质谱-程序升温表面反应（MS-TPSR）等技术研究了Ni／α-Al2O3催化剂上甲烷催化部分氧化制合成气（POM）的反应机理．结果表明,NiO上CH4不能解离产生H2只有当NiO被CH4还原为Ni0后,CH4才能解高产生H2,Ni0是CH4活化和POM反应的活性相;POM反应机理遵循直接氧化机理,CH4和O2均在Ni0上活化,活化过程形成的Ni…C和Niδ…Oδ物种是反应历程中的关键物种,Niδ …Oδ物种高选择性地与CH4解离产生的碳物种Ni…C反应生成CO．     

担载型钌催化剂吸附CO性能的原位红外研究

用原位红外研究了ＣＯ的吸附与脱附，ＣＯ／Ｈ２的共吸附及反应，考察了焙烧温度对Ｒｕ／Ａｌ２Ｏ３及Ｒｕ／ＳｉＯ２催化剂的影响，结果表明，经不同温度焙烧的催化剂样品，其吸附性能有很大差别。随着焙烧温度的升高，金属－载体相互作用增强，导致ＣＯ吸附量减少。Ｒｕ／Ａｌ２Ｏ３吸附的ＣＯ较稳定，而Ｒｕ／ＳｉＯ２吸附的ＣＯ在高温易脱附。各不同ＣＯ吸会态间、多重态更易发生反应。在未焙烧的Ｒｕ／ＳｉＯ２低ＣＯ／Ｈ２反应     

Studies on the Performance and Structure of Supported Catalysts for the Partial

The catalytic properties of several supported metal catalysts on different carriers were studied in the partial oxidation of methane (POM) to syngas. In our experiment, supported noble metal catalysts exhibited better performance than the other supported transition metal catalysts. The catalyst performances were significantly influenced by the d-electron configuration of the active metal components and the dispersion of active metal components on the support. A catalyst with a moderate number of unpaired electrons in the d-orbital of the active metal support without obvious acidity or redox activity (e.g. MgO) was suitable for POM performance. The Rh/SiO2 catalyst was the best in the POM reaction, among those investigated. Reaction conditions apparently also affected the POM performance of the catalyst. The conversion of methane and the selectivity for CO increased with the reaction temperature, and a high CH4/O2 ratio was not beneficial for POM performance.     

Studies on the Performance and Structure of Supported Catalysts for the Partial Oxidation of Methane to Syngas

The catalytic properties of several supported metal catalysts on different carriers were studied in the partial oxidation of methane (POM) to syngas. In our experiment, supported noble metal catalysts exhibited better performance than the other supported transition metal catalysts. The catalyst performances were significantly influenced by the d-electron configuration of the active metal components and the dispersion of active metal components on the support. A catalyst with a moderate number of unpaired electrons in the d-orbital of the active metal support without obvious acidity or redox activity (e.g. MgO) was suitable for POM performance. The Rh/SiO2 catalyst was the best in the POM reaction, among those investigated. Reaction conditions apparently also affected the POM performance of the catalyst. The conversion of methane and the selectivity for CO increased with the reaction temperature, and a high CH4/O2 ratio was not beneficial for POM performance.     

甲烷部分氧化制合成气Ⅰ．催化剂设计

在已有的关于甲烷催化部分氧化和催化氧化资料的基础上，假设了一个甲烷部分氧化反应的机理，并据此提出了催化剂设计的原则．在分析了Ｏ２，ＣＯ和Ｈ２等在金属表面上的吸附热的基础上，得出如下结论：金属Ｎｉ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕ和Ｉｒ可作为甲烷部分氧化催化剂的主要组分，Ｃｕ将是最佳助剂，具有较好的氢溢流功能的Ａｌ２Ｏ３可作为最佳载体     

Ni/Al2O3催化剂上甲烷部分氧化制合成气反应机理

用变应答／质谱在线检测技术研究了Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气的反应要理，研究结果指出，在常压９７３Ｋ条件下，Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气按直接氧化机理进行，Ｈ２和Ｃ烛甲烷部分氧化的一次产物，其主要反应可表示如下：１．ＣＨ４＋ｘＮｉ－ＮｉｘＣ＋２Ｈ２，２．Ｏ２＋２Ｎｉ－２ＮｉＯ，３．ＮｉｘＣ＋ＮｉＯ－ＣＯ＋（ｘ＋１）Ｎｉ。     

金属-载体相互作用对CH4/CO2重整反应中Rh基催化剂抗积炭性能的影响

考察了Rh/Al2O3,Rh/SiO2和Rh/CeO2催化剂上金属-载体间相互作用对CH4/CO2重整反应抗积炭性能的影响,并与反应前后催化剂的程序升温还原和程序升温氧化(TPO)测试结果相关联.实验发现,Rh与Al2O3和SiO2载体间的相互作用越强,催化剂还原后Rh的分散度越高,晶粒越小,高分散的Rh表面生成的碳物种CHx越多,其作为活泼的反应中间体越易与CO2反应生成CO和H2.而游离态的Rh还原后晶粒较大,生成的碳物种与CO2反应能力较低,从而导致催化剂失活.TPO和CO2脉冲实验结果表明,反应过程中Rh/CeO2催化剂上反应生成的CHx物种比Rh/Al2O3和Rh/SiO2上的CHx物种更活泼.同时由于Rh-CeO2间独特的相互作用,部分CeO2还原后生成CeO2-x和氧空位,促进CO2分子的活化解离,导致生成的表面氧容易与CHx反应,从而抑制催化剂积炭.     

Product oriented oxidative bromination of methane over Rh/SiO2 catalysts

Rh/SiO2 was prepared for the oxidative bromination of methane. The catalyst was prepared by calcination at different temperatures and for different times to obtain catalysts with different specific surface areas for the purposes of producing either CH3Br or CH3Br and CO. It was found that the catalyst having a low specific surface area (calcined at relatively high temperature) favors the selective oxidation of methane to prepare CH3Br, while the catalyst having a high specific surface area favors the deeper partial oxidation of methane, which is good for CH3Br and CO preparation. The 650 h on stream life-time test revealed that the catalytic performance of the 0.4Rh/SiO2--900-10 catalyst was excellent. Both methane conversion and CH3Br selectivity kept increasing trends during the life-time test. No matter how serious was the Rh leaching during the reaction, the 0.4Rh/SiO2--900-10 catalyst did not deactivate at all.     

Product oriented oxidative bromination of methane over Rh/SiO_2 catalysts

Rh/SiO2 was prepared for the oxidative bromination of methane. The catalyst was prepared by calcination at different temperatures and for different times to obtain catalysts with different specific surface areas for the purposes of producing either CH3Br or CH3Br and CO. It was found that the catalyst having a low specific surface area (calcined at relatively high temperature) favors the selective oxidation of methane to prepare CH3Br, while the catalyst having a high specific surface area favors the deeper partial oxidation of methane, which is good for CH3Br and CO preparation.The 650 h on stream life-time test revealed that the catalytic performance of the 0.4Rh/SiO2-900-10 catalyst was excellent.Both methane conversion and CH3Br selectivity kept increasing trends during the life-time test.No matter how serious was the Rh leaching during the reaction,the 0.4Rh/SiO2-900-10 catalyst did not deactivate at all.     

Rh基催化剂上CO加氢制C2含氧化物的原位红外光谱研究

 用原位红外光谱考察了Rh-Mn-Li-Fe/SiO2和Rh/SiO2催化剂表面上CO的吸附态及CO加氢反应过程中吸附物种的变化. 结果表明,CO在Rh/SiO2催化剂上仅有线式吸附态存在,而CO在Rh-Mn-Li-Fe/SiO2催化剂上既有线式吸附态存在,又有孪生吸附态存在. 这说明Rh-Mn-Li-Fe/SiO2催化剂中Rh的分散度较高. 经CO加氢反应(3.0 MPa,593 K)后,在Rh-Mn-Li-Fe/SiO2催化剂上可观测到C2含氧化物前驱物种的吸收谱带,而在Rh/SiO2催化剂上未观测到相应的谱带; CO在这两种催化剂上主要以线式吸附态存在,孪生吸附态基本消失. 结合催化剂对CO加氢的催化性能,可以认为线式吸附的CO对生成C2含氧化物有贡献. Rh-Mn-Li-Fe/SiO2催化剂的高活性是由于助剂的存在削弱了其表面吸附CO的 C-O键,促进了CO的活化,从而有利于C2含氧化物前驱物的生成.     

Rh/SiO_2催化剂上甲烷部分氧化制合成气反应机理的研究(英文)

运用ＴＰＳＲ、ＴＲ－ＦＴＩＲ和化学捕获技术（ＣＨ３Ｉ作捕获剂）,探讨了Ｒｈ／ＳｉＯ２催化剂上的ＰＯＭ反应机理,由此提出热分解氧化机理,认为ＣＨｘ（ｘ＝１～３）和ＣＨｘＯ（ｘ＝１～３）可能是反应物种。     

Partial oxidation of dimethyl ether to H2/syngas over supported Pt catalyst

Dimethyl ether （DME） is a non-toxic fuel with high H/C ratio and high volumetric energy density, and could be served as an ideal source of H2/syngas production for application in solid oxide fuel cells （SOFC）. This study presents results of DME partial oxidation over a 1.5 wt% Pt/Ce0.4Zr0.6O2 catalyst under the condition of gas hourly space velocity （GHSV） of 15000-60000 ml/（g·h）, molar ratio of O2/DME of 0.5 and 500-700 ℃, and this temperature range was also the operation temperature range for intermediate temperature SOFC. The results indicated that the catalyst showed good activity for the selective partial oxidation of DME to H2/syngas. Under the working conditions investigated, DME was completely converted. Increase in reaction temperature enhanced the amount of syngas, but lowered the H2/CO ratio and yield of methane; while increase in reaction GHSV resulted in only slight variation in the distribution of products. The good catalytic activity of Pt supported on Ce0.4Zr0.6O2 for the partial oxidation of DME may be directly associated with the good oxygen storage capacity of the support, which is worth of further investigation to develop materials for application in SOFC.     

焙烧温度对NiO/δ-Al2O3催化剂性能的影响

应用ＸＲＤ,ＴＰＲ,Ｈ２－ＴＰＤ技术研究焙烧温度对ＮｉＯ／δ－Ａｌ２Ｏ３催化剂性能的影响。结果表明,随着焙烧温度的增高,ＮｉＯ与载体Ａｌ２Ｏ３之间相互作用逐渐增强,直至最后生成ＮｉＡｌ２Ｏ４尖晶石。同时表明,随着焙烧温度的提高,催化剂的还原温度明显增高。另外,ＴＰＲ结果还表明ＮｉＡｌ２Ｏ４仅仅是与载体发生强相互作用的那部分ＮｉＯ进一步进入Ａｌ２Ｏ３晶格的结果,而游离态的ＮｉＯ不参与形成ＮｉＡｌ２Ｏ     

Partial Oxidation of Methane to Syngas Using Lattice Oxygen of La1-xSrxFeO3

Catalytic partial oxidation of methane to syngas using the lattice oxygen of La1-xSrxFeO3 perovskite oxide catalysts in place of molecular oxygen was studied. La1-xSrxFeO3 (x＝0, 0.1, 0.2,0.5) perovskite oxides were prepared by the "auto-combustion method". XRD analysis showed that all La1-xSrxFeO3 samples have a single-phase perovskite-type oxide. The redox properties of the catalysts were investigated by temperature programmed reduction with hydrogen (H2-TPR). Reducibility of the catalysts increase with the increasing of the Sr2+ content. The oxygen species of the catalysts and their reaction with CH4 were studied by the temperature programmed surface reaction (CH4-TPSR). In the absence of gas phase oxygen, there exist two kinds of oxygen species on the catalysts. One kind of the oxygen species with strong oxidative ability is produced first, which can oxidize CH4 completely to CO2 and H2O.Then, the second oxygen species with weak oxidative ability is formed, which can oxidize CH4 partially to CO and H2 with high selectivity. The number of the oxygen species with strong oxidative ability in the CH4-TPSR tends to become zero at low x values (x≤0.1). Under suitable reaction conditions, switching alternatively the reactions of 11% O2-Ar and 11% CH4-He over a La0.sSr0.2FeO3 catalyst at 900 ℃ allows methane to be selectively converted to synthesis gas (CH4 conversion ～90%, CO selectivity ＞93%) using the lattice oxygen of the perovskite oxide catalyst in a redox mode.     

甲烷部分氧化制合成气反应Pt/Al_2O_3和Pt/CeO2/Al_2O_3催化剂的研究(英文)

研究了Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３催化剂对甲烷部分氧化制合成气反应的催化活性，发现Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３显示了比Ｐｔ／Ａｌ２Ｏ３更高的甲烷转化率和合成气选择性。用Ｈ２ＴＰＲ，Ｈ２ＴＰＤ，ＳＥＭ和ＸＲＤ等手段和技术对催化剂进行了表征。ＣｅＯ２与Ｐｔ之间存在较强的相互作用（ＳＭＳＩ），这种作用促进了Ｐｔ在催化剂表面的分散，抑制了Ｐｔ在催化剂表面的迁移，大大降低了催化剂在反应中的完全燃烧活性，提高了催化剂的部分氧化活性和选择性，避免了因催化剂床层局部温度过高而导致催化剂活性下降或失活，提高了催化剂的稳定性。同时，在反应过程中，ＣｅＯ２通过促进水蒸气变换反应（ＷＧＳＲ）的进行使反应体系迅速达到平衡，提高了催化剂对Ｈ２的选择性。     

Syngas Production by Methane Reforming with Carbon Dioxide on Noble Metal Catalysts

A series of noble metal catalysts (Ru, Rh, Ir, Pt, and Pd) supported on alumina-stabilized magnesia (Spinel) were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.     

甲烷在Ni/TiO2催化剂表面的活化

考察了Ni/TiO2催化剂甲烷部分氧化和二氧化碳重整制合成气的反应活性,实验表明,以TiO2为载体的镍系催化剂对于甲烷部分氧化制合成气反应具有较好的活性,尤其对H2的选择性较高,对二氧化碳重整制合成气反应具有较好的低温反应活性.采用脉冲-质谱在线分析等技术,在无气相氧条件下向Ni/TiO2催化剂脉冲CH4,发现甲烷在催化剂表面的活化（转化）及其氧化产物的选择性与金属催化剂表面氧的浓度密切相关.CH4与Ni/TiO2催化剂作用过程中存在明显的氢溢流和氧溢流现象,可能是这种溢流效应使得Ni/TiO2催化剂具有良好的反应活性和抗积碳性能.     

甲烷在Ni/TiO_2催化剂表面的活化

考察了Ｎｉ／ＴｉＯ２催化剂甲烷部分氧化和二氧化碳重整制合成气的反应活性,实验表明,以ＴｉＯ２为载体的镍系催化剂对于甲烷部分氧化制合成气反应具有较好的活性,尤其对Ｈ２的选择性较高,对二氧化碳重整制合成气反应具有较好的低温反应活性．采用脉冲－质谱在线分析等技术,在无气相氧条件下向Ｎｉ／ＴｉＯ２催化剂脉冲ＣＨ４,发现甲烷在催化剂表面的活化（转化）及其氧化产物的选择性与金属催化剂表面氧的浓度密切相关．ＣＨ４与Ｎｉ／ＴｉＯ２催化剂作用过程中存在明显的氢溢流和氧溢流现象,可能是这种溢流效应使得Ｎ／ＴｉＯ２催化剂具有良好的反应活性和抗积碳性能．