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1.
Rh/SiO2催化剂上甲烷部分氧化制合成气反应 总被引:4,自引:0,他引:4
利用程序升温脱附、程序升温还原、程序升温表面反应、程序升温反应和化学捕获反应等手段,对Rh/SiO2催化剂上甲烷部分氧化制合成气反应进行了研究.结果表明,Rh/SiO2催化剂上甲烷部分氧化制合成气机理属于热解-氧化反应机理.甲烷首先在催化剂上发生解离吸附,产生具有不同H/C比的化学吸附物种CHx(x=1~3).其中,具有较高H/C比的CHx可能是甲烷部分氧化反应的活性物种,而具有较低H/C比的CHx可能是催化剂上积碳并导致催化剂失活的来源.活性物种CHx在活性氧物种的作用下,生成含氧中间体物种CHxO或继续脱氢.含氧中间体物种进一步分解,即生成CO和H2;CO2也可由CHx或CHxO物种进一步氧
化生成. 相似文献
2.
In-Situ FT-IR Investigation of Partial Oxidation of Methane to Syngas over Rh/SiO_2 Catalyst
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Tinghua Wu Dongmin Lin Ying Wu Xiaoping Zhou Qiangu Yan Weizheng Weng Huilin Wan 《天然气化学杂志》2007,16(3)
Partial oxidation of methane to syngas(POM)over Rh/SiO_2 catalyst was investigated using in-situ FT-IR.When methane interacted with 1.0wt%Rh/SiO_2 catalyst,it was dissociated to adsorbed hydrogen and CH_x species.The adsorbed hydrogen atoms were transferred to SiO_2 surface by"spill-over"and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO_2 catalyst using in-situ FT-IR.It was found that CO_2 was formed before CO could be detected when CH_4 and O_2 were introduced over the preoxidized Rh/SiO_2 catalyst,whereas CO was detected before CO_2 was formed over the prereduced Rh/SiO_2 catalyst. 相似文献
3.
Tinghua Wu Dongmin Lin Ying Wu Xiaoping Zhou Qiangu Yan Weizheng Weng Huilin Wan 《天然气化学杂志》2007,16(3):316-321
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. 相似文献
4.
利用1H MAS NMR技术,在甲烷部分氧化(POM)制合成气反应条件下研究了Rh/SiO2催化剂上氢与金属的相互作用及反应机理. 结果发现,氢气在Rh/SiO2上解离吸附后可能有四种存在形式: 化学位移为δ=-100~-120的可逆(αM)和不可逆(αI)吸附氢物种,δ=0~-100的“氢云”或“氢雾”形式的氢物种和δ=3.0的溢流氢物种. 溢流氢物种是由可逆吸附的氢物种和“氢云”或“氢雾”状态的氢物种溢流到SiO2上并弱吸附在桥式氧(Si-O-Si)附近而形成的. 溢流氢物种活化晶格氧,形成一种POM反应的活性氧物种OH-. 活性氧物种OH-反溢流到Rh上,并与CH4解离吸附在Rh上的CHx物种反应生成含氧中间物种CHxO. CHxO物种的化学位移为5~7. O2参与CHxO物种的进一步氧化,或补充溢流氢夺取桥式氧后形成的缺陷位上的晶格氧,在高温(973 K)反应条件下,O2可能优先补充缺陷位上的晶格氧,使CHx的氧化按表面反应机理进行. 相似文献
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用浸渍法制备了Pt/MgO催化剂,并采用X射线衍射、X射线光电子能谱、透射电子显微镜和程序升温表面反应等技术对催化剂进行了表征.考察了催化剂对甲烷部分氧化制合成气反应的催化性能.结果表明,Pt/MgO催化剂具有较高的催化活性和选择性,甲烷转化率与合成气选择性在120 h内保持稳定.以金属状态存在的Pt对甲烷分解具有较高的活性,从而使催化剂对甲烷部分氧化反应具有较高的催化活性.活性组分Pt的存在状态和分散状态非常稳定,而Pt/MgO催化剂具有较强的抗积碳能力,使得催化剂在甲烷部分氧化制合成气反应中具有较高的稳定性. 相似文献
6.
Ni/TiO2 catalyst was firstly used for the partial oxidation of methane to produce synthesis gas. The reaction was carried out in a fixed-bed continuous flow quartz reactor at atmospheric pressure. The flow rate was regulated by a mass controller with a space velocity of 1.5×105 h-1 and a CH4/O2 molar ratio of 2/1. Prior to the introduction of feed gas, the Ni/TiO2 catalyst was activated in flowing H2 at 700℃ for 30 min. TiO2 is known to be a poor support for partial oxidation because which can easily result in complete oxidation. But at 700℃, Ni/TiO2 catalyst exhibited a better performance than Ni/SiO2 and Ni/ZrO2. The conversion of methane was 81.5, and the selectivity of hydrogen and carbon monoxide were 93.4 and 89.4 respectively. After 6h of continuous reaction, the conversion of methane descended a little and then remained a steady yield on the whole,but the selectivity of H2 and CO gradually declined, as far as to a constant. The selectivity of H2 was always higher than that of CO and the ratio of H2/CO wouldn't change with the increasing of reaction time. 相似文献
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The partial oxidation reaction of mathane over reduced 10wt%Ni/SiO2 catalyst was studied at 600, 650, 700℃ by means of pulse and bond-order conservation Morse-potential (BOC-MP) methods. In the oxidation reaction of surface carbon deposited on the catalyst, it was observed that the product selectivity was subject to the reaction temperature and the selectivity of CO was increased with rasing temperature of CH4/O2, the same trend between CO selectivity and reaction temperature was also observed, implying that the partial oxidation of methane to syngas follows the pyrolysis mechanism under the reaction conditions. The BOC-MP calculation on the elementary reaction steps over Ni(111) surface indicates that the direct dissociation of CH4 without the involvement of surface oxygen is more likely to occur and the formation of CO from CH(s) occurs more readily than from C(s). 相似文献
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MicrowavedielectricheatingisfoundtobeanalternativeproceduretoconventionalconductiveheatingforintroducingenergyintocheInicalreactionsandseemstobeawell-suitedprocessforactivatingsolidcatalystS'-'.TheoriginofthendcrowavecouplingdielectricheatingIiesinthecapacityofanelectricfieldtopolarizechargesinamaterial.TheheatingeffectismoreemphasizedwhentheirradiatedmaterialhasastrongdipoIarcharacter.ThisisparticularlythecasewiththosecatalystswhosesupportisanoxidewithnumerouspoIarOHgroups.Moreover,whenpol… 相似文献
9.
分别采用柠檬酸络合法和直接分解法制备了Cr2O3催化剂, 采用XRD, BET, TPR, XPS, TEM和TGA表征了催化剂的物理化学性质, 在常压固定床石英管(内径5 mm)反应器中考察了Cr2O3催化剂对甲烷部分氧化反应的催化性能. 在500~750 ℃, V(CH4)∶V(O2)=2, 空速12×104 h-1的条件下, O2几乎完全转化, CH4转化率及H2和CO选择性随着温度的升高而增加. 700 ℃下CH4转化率及H2, CO选择性随着空速(6.0×104~24×104 h-1)的升高而增加. 在500 h稳定性实验中, 随着反应时间的延长, CH4转化率及H2, CO选择性缓慢下降, XRD, TEM和BET结果表明, 催化剂的活性下降与烧结和团聚有关, TGA分析表明催化剂具有良好的抗积炭性. 通过CH4脉冲反应, 推测在反应过程中CO, H2, CO2和H2O是直接生成的. 相似文献
10.
WU Ting-Hua YAN Qian-Gu CHAO Zi-Sheng LUO Chun-Rong YE Jian-Liang WAN Hui-Lin 《高等学校化学学报》2000,21(Z1):133
In our previous work, POM has been investigated by the pulse reaction with CH4 and CH4/O2 respectively, on Rh/SiO2 catalyst. Kinetic isotopic effect was also studied by using CD4 and CD4/O2. The results suggest that POM may proceed most possibly via a mechanism of surface carbon species reacting with surface oxygen. In the present work, 1H MAS NMR was utilized to investigate the POM mechanism in aiming of presenting additional evidence. 相似文献
11.
本文采用高温分解和焙烧硝酸盐的方法合成了一系列Ni基六铝酸盐催化剂BaNiyAl12-yO19-δ (y=0.1、0.3、0.6、0.9和1.0),并对它们在甲烷部分氧化制合成气反应中的催化性能、催化剂表面积碳及活性组分Ni流失等情况进行了考察。结果表明,该催化剂对甲烷部分氧化制合成气反应具有较好的催化活性,在850 ℃,甲烷转化率和CO选择性分别可达92%和95%。并且催化剂BaNiyAl12-yO19-δ (y=0.3)在100小时的POM反应后,催化剂表面积碳很少,积碳量仅为样品净重的0.8%,特别是100小时反应后,催化剂表面活性组分Ni没有发生流失。这种低积碳量和无活性组分Ni流失与催化剂结构中Ni与相邻原子间的强相互作用有关。 相似文献
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Fang-Fang ZHENG Qian LI Hong ZHANG Wei-Zheng WENG Xiao-Dong YI Yan-Ping ZHENG Chuan-Jing HUANG Hui-Lin WAN 《物理化学学报》2017,33(8):1689-1698
以乙酰丙酮铑(Rh(acac)_3)和乙酰丙酮钐(Sm(acac)_3)为前驱体,用浸渍法制备了Rh/SiO_2和Rh-Sm_2O_3/SiO_2催化剂。采用原位红外光谱、热重分析、低温N_2吸附、X射线粉末衍射、高分辨透射电子显微镜、H_2-程序升温还原和X射线光电子能谱等实验技术对催化剂的制备过程,比表面积和物相以及Rh与Sm_2O_3间的相互作用进行了表征,并以甲烷部分氧化制合成气为目标反应对催化剂的稳定性进行了考察。研究表明:以Rh(acac)_3和Sm(acac)_3为前驱体采用简单的浸渍法即可制备出Rh平均粒径为2.3 nm且具有良好抗烧结性能的Rh-Sm_2O_3/SiO_2催化剂。在浸渍过程中乙酰丙酮化合物通过与SiO_2表面羟基形成氢键而负载于载体表面。Sm(acac)_3在SiO_2表面的单层负载量(质量分数)约为31%,对应于Sm_2O_3的质量分数约为15%,只要Sm(acac)_3的质量分数低于这一阈值,均可保证分解后生成的Sm_2O_3以高分散形式负载于SiO_2上,且不会因高温(800°C)焙烧而团聚。高分散于SiO_2表面的Sm_2O_3与Rh之间存在强的相互作用,可显著提高Rh的分散度,防止其在高温反应条件下烧结,进而使低Rh负载量的催化剂表现出良好的甲烷部分氧化制合成气反应活性和稳定性。 相似文献
14.
甲烷部分氧化制合成气的研究 总被引:7,自引:1,他引:7
考察了镍基和钴基催化剂催化甲烷在自放热条件下部分氧化制合成气。结果表明,在较高的空速条件下,反应一旦引发即可停止供热,仅靠反应自身放出的热量就能维持反应的继续进行:Ni/La2O3催化剂中的镍负载量大于10%后,镍负载量对催化活性无明显的影响;CH4的转化率及H2和CO的选择性均随空速和反应温度的增加而提高;对Ni/ZrO2和Co/ZrO2催化剂,反应进行到6-12h时,CH4转化经最高;但对Ni 相似文献
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发烟硫酸中Pd/C催化甲烷选择氧化制甲醇 总被引:2,自引:0,他引:2
以PdCl2为前驱体,采用浸渍法制备了Pd/C催化剂,并在发烟硫酸中考察了其催化甲烷选择氧化反应的性能,采用X射线粉末衍射、X射线光电子能谱、高分辨透射电镜和CO吸附等方法对催化剂进行了表征. 甲烷选择氧化反应得到的主产物硫酸单甲酯经水解后得到甲醇,在5%Pd/C催化剂、Pd用量30 μmol、反应温度180 ℃、反应压力4.0 MPa、反应时间 4 h 和发烟硫酸中SO3含量为50%的优化工艺条件下,甲烷转化率为23.6%, 甲醇的选择性和收率分别为69.5%和16.4%, 在一定程度上可实现催化剂的多次重复使用. Pd/C催化剂上的甲烷选择氧化反应可能遵循亲电取代机理,催化性能与Pd负载量、Pd粒子尺寸和分散度等有关. 相似文献
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Partial oxidation of methane (POM) was investigated over Rh/SiO2 catalyst using several techniques combined with MS, such as temperature programmed desorption (TPD), temperature programmed reduction (TPR), temperature programmed surface reaction (TPSR), temperature programmed reaction, and CH3I chemical trapping reaction. 相似文献
19.
Ir/SiO2上甲烷部分氧化制合成气反应的原位时间分辨红外和原位Raman光谱表征 总被引:2,自引:0,他引:2
采用原位时间分辨红外光谱和原位显微Raman光谱技术对Ir/SiO2上甲烷部分氧化(POM)制合成气反应的初级产物和反应条件下催化剂表面物种进行了跟踪考察,实验结果表明,在H2预还原的新鲜Ir/SiO2表面,CO是V(CH4):V(O2):V(Ar)=2:1:45混合气反应的初级产物,因而甲烷的直接氧化过程是CO生成的主要途径;而在稳态反应条件下,CO生成的途径可能主要来自CO2和H2O与催化剂表面积碳物种(CHx)和/或CH4的反应.催化剂上生成的积碳可能是导致稳态条件下Ir/SiO2上POM反应机理不同于H2预还原的新鲜催化剂的主要原因. 相似文献