FeM双金属用于甲烷催化裂解制纯氢气和碳纳米材料

doi:10.16085/j.issn.1000-6613.2020-2226

摘要/Abstract

摘要：

采用熔融法以铁、钼、铜和钨硝酸盐为原料，制备出一系列的Fe_xM_y（M=Mo、Cu、W）双金属催化剂。首先考察了一系列的Fe₁₅M₁（M=Mo、Cu、W）双金属催化剂的甲烷催化裂解（CDM）活性，Fe₁₅Mo₁的催化活性远高于Fe₁₅Cu₁和Fe₁₅W₁。通过比表面积测试（BET）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）和拉曼光谱（Raman）等分析方法对Fe₁₅M₁的物理特性、结构组成、还原特性和副产物碳纳米材料（CNMs）的石墨化度等进行表征。进一步考察了金属Mo的掺杂量和焙烧温度对Fe_xMo_y双金属催化剂的甲烷转化率和碳产率的影响。Fe₁Mo₁表现出优异的催化性能，其碳产率（6g_C/g_cat）高于纯Fe的碳产率（4.35g_C/g_cat）。XRD和X射线光电子能谱（XPS）分析表明，Fe₁Mo₁双金属形成Fe₂(MoO₄)₃相，提高了其催化活性和稳定性；透射电镜（TEM）结果表明，Fe₁Mo₁催化剂CDM反应后的CNMs为竹节状的碳纳米管。

关键词: 甲烷, 裂解, 催化剂, 制氢, 碳纳米材料

Abstract:

A series of Fe_xM_y (M=Mo, Cu, W) bimetallic catalysts were prepared by the fusion method using iron, molybdenum, copper and tungsten nitrate as raw materials. Fe₁₅M₁ (M=Mo, Cu, W) bimetallic catalysts were synthesized to investigate their catalytic decomposition of methane (CDM) activity. Results indicated that the catalytic activity of Fe₁₅Mo₁ was much higher than that of Fe₁₅Cu₁ and Fe₁₅W₁. The physical characteristics, structural composition, reduction characteristics and the graphitization of by-product carbon nano materials (CNMs) were characterized by means of specific surface area (BET), X?ray powder diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR) and Raman spectra, respectively. Then, the effects of Mo doping and calcination temperature on the methane conversion and carbon yield over the Fe_xMo_y catalysts for CDM were further investigated. It was found that, the Fe₁Mo₁ catalyst had the best catalytic activity and stability, and its carbon yield (6g_C/g_cat) was higher than that of pure Fe (4.35g_C/g_cat). XRD and X-ray photoelectron spectroscopy (XPS) results showed that Fe₂(MoO₄)₃ phase was formed in Fe₁Mo₁, which increased the catalytic activity and stability. Transmission electron microscope (TEM) results indicated that the deposited CNMs over the spent Fe₁Mo₁ catalyst were bamboo-like carbon nano tubes.

Key words: methane, decomposition, catalyst, hydrogen production, carbon nano materials

中图分类号:

O611.65

钱敬侠, 陈天文, 刘大斌, 周吕. FeM双金属用于甲烷催化裂解制纯氢气和碳纳米材料[J]. 化工进展, 2021, 40(11): 6102-6112.

QIAN Jingxia, CHEN Tianwen, LIU Dabin, ZHOU Lyu. Methane decomposition to produce pure hydrogen and carbon nano materials over FeM catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6102-6112.

图/表 18

表1 新鲜催化剂的物理特性

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₁₅Cu₁	0.4	—	—
Fe₁₅W₁	16.4	0.09	29.1

图1 新鲜催化剂的XRD图

图2 反应后催化剂的XRD图

图3 新鲜催化剂的H2-TPR曲线

图4 反应后催化剂的拉曼光谱图

图5 FeM催化剂的甲烷转化率（反应条件为m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL·min-1纯甲烷；Fe15Cu1的反应条件为m=1.6g，T=900℃，GHSV=1.8L·gcat-1·h-1，50mL·min-1纯甲烷）

表2 新鲜催化剂FexMoy的物理特性

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₅Mo₁	8.8	0.06	33.5
Fe₃Mo₁	7.8	0.06	38.7
Fe₁Mo₁	0.7	0.01	38.8
Fe₁Mo_1.5	0.07	—	—

图6 FeM催化剂的碳产率（反应条件为m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL·min-1纯甲烷；Fe15Cu1的反应条件为m=1.6g，T=900℃，GHSV=1.8L·gcat-1·h-1，50mL·min-1纯甲烷）

图7 新鲜催化剂FexMoy的XRD图

图13 Mo的添加量对甲烷转化率的影响（m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL/min纯甲烷）

图14 FexMoy催化剂的碳产率（m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL/min纯甲烷）

图8 反应后催化剂FexMoy的XRD图

图9 不同焙烧温度的Fe15Mo1的XRD图

图10 新鲜催化剂Fe1Mo1的XPS总谱图及Fe 2p、Mo 3d、O 1s的高分辨图谱

表3 Fe1Mo1的XPS谱图中每种元素的质量分数分析 (%)

项目	Fe 2p				O 1s	Mo 3d
项目	Fe 2p_3/2	Fe 2p_3/2卫星峰	Fe 2p_1/2	Fe 2p_1/2卫星峰	O 1s	Mo 3d_5/2	Mo 3d_3/2
Fe₂O₃	—	—	—	—	3.6	—	—
MoO₃	—	—	—	—	18.6	—	—
Fe₂(MoO₄)₃	—	—	—	—	69.0	—	—
表面吸附氧					8.8
Fe₂O₃/Fe₂(MoO₄)₃	48.9	14.6	28.1	8.4	—	—	—
MoO₃/Fe₂(MoO₄)₃	—	—	—	—	—	60.4	39.6

图11 反应后催化剂Fe1Mo1的XPS总谱图及C 1s的高分辨图谱

图12 反应后催化剂Fe1Mo1碳纳米管的TEM图（m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL·min-1纯甲烷）

图15 焙烧温度对碳产率的影响（m=1g，T=900℃，GHSV=6L·gcat-1·h-1，100mL/min纯甲烷）

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