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61.
62.
Pd/ZrO2是甲烷低温燃烧研究较为广泛的催化剂,其中载体ZrO2对稳定PdO起到了重要作用。采用水热法合成了纯相的M-ZrO2和T-ZrO2,然后采用浸渍法制备了Pd/M-ZrO2和Pd/T-ZrO2催化剂,并考察了不同晶型ZrO2对催化剂的活性和稳定性的影响。结果表明,Pd/M-ZrO2催化剂的活性和稳定性明显优于Pd/T-ZrO2。结合XRD、TEM和TPO表征结果,发现Pd/M-ZrO2活性高的原因是PdO分散性更好,Pd/M-ZrO2较好的稳定性与PdO和ZrO2的作用方式有关。 相似文献
63.
Nanostructured -y-A12O3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, N2 adsorption-desorption, TPR, TPO, TPH, NH3-TPD and SEM techniques. The BET analysis showed a high surface area of 204 m2.g-1 and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The BET results revealed that addition of lanthanum oxide to aluminum oxide decreased the specific surface area. In addition, TPR results showed that addition of lanthanum oxide increased the reducibility of nickel catalyst. The catalytic evaluation results showed an increase in methane conversion with increasing lanthanum oxide to 3 mol% and further increase in lanthanum content decreased the catalytic activity. TPO analysis revealed that the coke deposition decreased with increasing lanthanum oxide to 3 mol%. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Addition of steam and Oxide to drv reformin feed increased the methane conversion and led to carbon free ooeration in combined orocesses. 相似文献
64.
《天然气化学杂志》2014,(6):761-770
Highly coke-resisting ZrO2-decorated Ni/A1203 catalysts for CO methanation were prepared by a two-step process. The support was first loaded with NiO by impregnating method and then modified with ZrO2 by deposition-precipitation method (IM-DP). Nitrogen adsorption- desorption, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetdc analysis, H2 temperature- programmed reduction and desorption, NH3 temperature-programmed desorption, and zeta potential analysis were employed to characterize the samples. The results revealed that, compared with the catalysts with the same composition prepared by co-impregnation (CI) and sequential impregnation (SI) methods, the Ni/A1203 catalyst prepared by IM-DP showed much enhanced catalytic performance for syngas methanation under the condition of atmospheric pressure and a high weight hourly space velocity of 120000 mL.g-1 .h-1. In a 80 h life time test under the condition of 300-600 ~C and 3.0 MPa, this catalyst showed high stability and resistance to coking, and the amount of deposited carbon was only 0.4 wt%. On the contrary, the deposited carbon over the catalyst without ZrO2 reached 1.5 wt% after a 60 h life time test. The improved catalytic performance was attributed to the selective deposition of ZrO2 nanoparticles on the surface of NiO rather than A1203, which could he well controlled via changing the electrostatic interaction in the DP procedure. This unique structure could enhance the dissociation of CO2 and generate surface oxygen intermediates, thus preventing carbon deposition on the Ni particles in syngas methanation. 相似文献
65.
甲烷和二氧化碳在煤焦上反应制备合成气实验研究 总被引:3,自引:1,他引:2
以煤与甲烷共转化制备合成气的研究为背景,通过考察固定床反应器上甲烷和二氧化碳分别在石英砂、煤灰和煤焦上的反应过程,证实了煤焦中的碳结构在共转化过程中对甲烷转化具有催化作用。同时考察了反应温度(1073K~1223K)、CH4/CO2比(0.33~3.00)和气固接触时间等工艺条件对甲烷转化率、气相产物中H2/CO比的影响。结果表明,甲烷的转化率随着反应温度和气固接触时间的增加而增大,随CH4/CO2比的增加而减小。在考察范围内甲烷的转化率最高达到了86%。反应物中CH4/CO2比的改变可以起到调节产品气中H2/CO比的作用,0.4~2.0调节。 相似文献
66.
采用分步浸渍法制备了NiO/α-Al2O3、NiO-CuO/α-Al2O3和NiO-La2O3/α-Al2O3三种催化剂,运用程序升温表面反应(TPSR)技术考察了助剂CuO和La2O3对NiO/α-Al2O3甲烷催化部分氧化(CPOM)反应引发过程的影响。结果表明,无论是否经过预还原处理,NiO/α-Al2O3催化剂在CH4/O2混合气氛下进行程序升温表面反应(CH4/O2-TPSR)时,即使升高到910℃也不能引发CPOM反应。添加助剂CuO或La2O3后,NiO-CuO/α-Al2O3和NiO-La2O3/α-Al2O3催化剂在CH4/O2-TPSR过程中均可以引发CPOM反应。原因分别是CuO促进了CH4对NiO的还原以及抑制了O2对Ni0的再氧化,La2O3减小了Ni晶粒粒径和还原时扩散阻力促进NiO的还原。 相似文献
67.
68.
The title compound [Cu2(μ2-dppm)2(MeCN)2(μ2-MeCN)](ClO4)2·MeCN (dppm = bis(diphenylphosphino)methane) has been prepared and characterized. It crystallizes in the monoclinic system,space group P21/n,with a = 11.904(6),b = 20.755(11),c = 24.744(13)A,β = 98.226(12)°,C58H56Cl2Cu2N4O8P4,Mr = 1258.93,V = 6051(5) A^3,Z = 4,Dc = 1.382 g/cm^3,μ = 9.52 mm^-1,F(000) = 2592,R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I 〉 2σ(I). Each Cu(I) center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands,one nitrogen atom from a terminally coordinated acetonitrile molecule,and another nitrogen atom from a μ2-acetonitrile molecule. The two Cu(I) centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a 'chair-like' configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm. 相似文献
69.
采用广义梯度近似 (GGA) 的密度泛函理论 (DFT) 并结合平板模型, 研究了 CH4 在清洁 Pd(111) 及 O 改性的 Pd(111) 表面发生 C朒 键断裂的反应历程. 优化了裂解过程中反应物、过渡态和产物的几何构型, 获得了反应路径上各物种的吸附能及反应的活化能. 结果表明, CH4 采用一个 H 原子指向表面的构型在 Pd(111) 表面的顶位吸附, CH3 的最稳定的吸附位置为顶位, OH, O 和 H 的最稳定吸附位置均为面心立方. CH4 在清洁 Pd(111) 表面裂解的活化能为 0.97 eV, 低于它在 O 原子改性 (O 没有参与反应) 的 Pd(111) 表面的活化能 1.42 eV, 说明表面氧原子抑制了 CH4 中 C朒 键的断裂. 当亚表面 O 原子和表面 O 原子 (O 参与反应) 共同存在时, C朒 键断裂的活化能为 0.72 eV, 低于只有表层氧存在时的活化能 (1.43 eV), 说明亚表面的 O 原子对 CH4 分子的活化具有促进作用. CH4 在 O 原子改性的 Pd(111) 表面裂解生成 CH3 和 H, 以及生成 CH3 和 OH 的反应活化能分别为 1.42 和 1.43 eV, 说明 CH4 在 O 原子改性的 Pd(111) 表面发生这两种反应的难易程度相当. 相似文献
70.
Two novel triazolyl derivatives with biphenyl links, namely 4,4-bis(1,2,4-triazol-1-ylmethyl)biphenylene 1 and 4,4-bis(3,5-dimethyl-1,2,4-triazol-1-ylmethyl)biphenylene 2, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Compounds 1·H2O·HCl and 2·2H2O·2HCl crystallize in the monoclinic system with space group C2/c and P21/c, respectively. The dihedral angles of the two phenyl rings are 30.26(6)° in 1·H2O·HCl, while co-planar (0.00(7)°) in 2·2H2O·2HCl. In 1·H2O·HCl, the N-H…O hydrogen bonds link 1 to form chain-like structures which are further connected by O-H…Cl, C-H…Cl, C-H…O and π-π supramolecular interactions. The hydrogen bonds of O-H…Cl in 2·2H2O·2HCl provide distinguishing P/M helical chains along the b axis, and these chains are further connected by N-H…O hydrogen bonds to generate a 2D structure. Compounds 1 and 2 in methanol solution show much stronger emission bands at 319 nm than biphenyl at 316 nm under excitation at 260 nm. 相似文献