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物理化学学报  2019, Vol. 35 Issue (6): 607-615    DOI: 10.3866/PKU.WHXB201805054
论文     
Ni/SiO2在甲烷部分氧化反应中的稳定性:W修饰的影响
连孟水,王雅莉,赵明全,李倩倩,翁维正,夏文生*(),万惠霖*()
Stability of Ni/SiO2 in Partial Oxidation of Methane: Effects of W Modification
Mengshui LIAN,Yali WANG,Mingquan ZHAO,Qianqian LI,Weizheng WENG,Wensheng XIA*(),Huilin WAN*()
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摘要:

甲烷部分氧化制合成气反应(POM)是天然气、页岩气资源利用的重要途径之一,常用的Ni/SiO2催化剂在反应中易发生表面积炭而失活。为了解决这一问题,我们采用尿素沉淀法制备W修饰的Ni基催化剂,并考察其在POM反应中的稳定性和W的作用。结果表明,催化剂中适量W的存在可显著改善其POM反应稳定性。其原因为Ni-W作用修饰了Ni的化学态或其亲氧能力,从而改善了其表面抗积炭能力。此外,反应中催化剂表面形成的α-WC具有一定的抑制表面积炭形成的能力,且该α-WC具有良好的稳定性。

关键词: 甲烷部分氧化稳定性Ni基催化剂钨修饰    
Abstract:

With the discovery and large-scale exploitation of natural gas resources such as shale gas and combustible ice, which are mainly composed of methane, their effective utilization has become a national strategic interest. Partial oxidation of methane (POM) to synthesis gas is one of the important methods for the utilization of natural gas and shale gas resources. The commonly used Ni/SiO2 catalyst for POM easily deactivates due to carbon deposition on the surface. To solve this problem, a urea precipitation method was employed in this work to prepare Ni-based catalysts modified with different amounts of tungsten (at W/Ni molar ratios of 0, 0.01, 0.03, 0.05, 0.07, and 0.10), and the catalyst stability in POM as well as the role of W were investigated. From characterizations such as X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS), we obtained the following results. The amount of W added to the Ni-based catalysts has a significant influence on their catalytic performances in POM and their physicochemical properties. The particle size of Ni in the catalysts decreases with W addition, and the Ni particle distribution on the support surfaces becomes more uniformed; however, the catalytic activity for POM is not significantly influenced. However, W-modified Ni-based catalysts show an increasing improvement in their stability in POM with increasing W/Ni molar ratio, with an optimum at the W/Ni molar ratio of 0.07; at the W/Ni molar ratio of 0.10, they exhibit a rapid deactivation in POM in a short time. Although interactions between Ni and SiO2 in the as-prepared catalysts are weak, the presence of adequate tungsten (W/Ni molar ratio of 0.05 and above) in the Ni-based catalysts can reduce the Ni particle size to some extent, and lead to the formation of strong interactions between Ni and W, which leads to an improvement in the dispersion of Ni on the support surface and imparts resistance for Ni particle growth in the POM reaction. The increased interaction between Ni and W changes the chemical state or oxygen affinity of Ni particles on the catalyst surfaces, and some of the partially oxidized Ni species (Niδ+) on the catalyst surfaces coexist with reduced Ni species (Ni0) during POM. Using an adequate amount of W-modified Ni catalysts results in almost no carbon deposition on the surfaces during POM, but using only a moderate amount results in good catalytic behavior and stability in POM. This finding suggests that the presence of W can not only enhance the anti-coking ability of the Ni-based catalysts and sustain their good stability in POM if the W content is low (i.e., W/Ni molar ratio of 0.07 and below), but also lead to the deactivation of W-modified catalysts in POM if the W content is high (i.e., W/Ni molar ratio of 0.10 and above), due to high oxygen affinity or the presence of more Ni species in oxidized form. In addition, α-WC (tungsten carbide) was identified using XRD to be formed on the surface of the moderate-amount W-modified Ni catalysts after POM, and it could inhibit or eliminate carbon deposition on the Ni-based catalyst surfaces. The catalytic performance evaluation of the catalysts in POM under a long time period confirmed that α-WC is stable.

Key words: Partial oxidation of methane    Stability    Ni based catalyst    Modification of tungsten
收稿日期: 2018-05-20 出版日期: 2018-07-11
中图分类号:  O643  
基金资助: 国家自然科学基金(21373169);教育部创新团队(IRT1036)
通讯作者: 夏文生,万惠霖     E-mail: wsxia@xmu.edu.cn;hlwan@xmu.edu.cn
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引用本文:

连孟水,王雅莉,赵明全,李倩倩,翁维正,夏文生,万惠霖. Ni/SiO2在甲烷部分氧化反应中的稳定性:W修饰的影响[J]. 物理化学学报, 2019, 35(6): 607-615, 10.3866/PKU.WHXB201805054

Mengshui LIAN,Yali WANG,Mingquan ZHAO,Qianqian LI,Weizheng WENG,Wensheng XIA,Huilin WAN. Stability of Ni/SiO2 in Partial Oxidation of Methane: Effects of W Modification. Acta Phys. -Chim. Sin., 2019, 35(6): 607-615, 10.3866/PKU.WHXB201805054.

链接本文:

http://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201805054        http://www.whxb.pku.edu.cn/CN/Y2019/V35/I6/607

图1  新鲜(A)及还原后(B)样品9NiWx/SiO2的XRD谱图 (a) 9Ni/SiO2; (b) 9NiW0.01/SiO2; (c) 9NiW0.03/SiO2; (d) 9NiW0.05/SiO2; (e) 9NiW0.07/SiO2; (f) 9NiW0.10/SiO2; (g) 9NiW/SiO2.
Sample ABET/(m2.g-1) Volume/(cm3.g—1) Aperture/nm DXRD/nm DTEM/nm
Fresh Reduced Used (10 h; 50 h) Reduced Used (10 h; 50 h)
SiO2 371.3 0.80 8.6 - - - - -
9Ni/SiO2 327.6 0.67 7.8 26.9 39.7 56.5; - 38.0 55.7; -
9NiW0.01/SiO2 311.3 0.65 7.7 24.7 36.6 46.6; - 36.7 42.2; -
9NiW0.03/SiO2 304.4 0.66 7.7 17.3 32.7 38.8; - 32.2 36.3; -
9NiW0.05/SiO2 296.0 0.61 7.2 11.0 30.9 35.1; - 28.1 33.6; -
9NiW0.07/SiO2 285.9 0.57 6.9 9.3 18.7 19.9; 21.3 18.6 20.0; 21.0
9NiW0.10/SiO2 276.2 0.58 7.0 9.9 22.1 22.7 a; - 19.1 20.6 a; -
表1  不同样品的比表面(ABET)、孔结构及反应前后Ni/NiO的粒径
图2  还原样品9NiWx/SiO2的TEM照片及粒径大小分布
图3  9NiWx/SiO2催化剂上POM反应性能随时间的变化
图4  9NiWx/SiO2催化剂反应10 h后的XRD谱
图5  9NiWx/SiO2催化剂反应10 h后的TEM照片及粒径大小分布
图6  9NiWx/SiO2催化剂的H2-TPR谱图
Catalysts Binding energy/eV [Ni2+]/[Ni0]
Ni0 Ni2+
9Ni/SiO2 852.4 855.6 0.25
9NiW0.07/SiO2 852.7 855.8 0.39
9NiW0.10/SiO2 853.0 856.2 0.59
9Ni/SiO2 used 852.4 855.7 0.30
9NiW0.07/SiO2 used 852.6 855.7 0.65
9NiW0.10/SiO2 used 852.7 855.8 3.01
表2  催化剂上Ni 2p3/2电子结合能及表面Ni物种组成分析
9Ni/SiO2 13.1 9NiW0.07/SiO2 0.0
9NiW0.01/SiO2 8.2 9NiW0.07/SiO2 * 0.0
9NiW0.03/SiO2 7.2 9NiW0.10/SiO2 0.0
9NiW0.05/SiO2 5.2
表3  POM反应(10 h,20 h)后催化剂表面积炭分析
图7  还原后(A)及反应后(B)的9NiWx/SiO2催化剂的XPS谱图
图8  9NiW0.07/SiO2催化剂上POM反应性能随时间(50 h)的变化
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