Research on promotion of Fe in Ni/SBA-16 catalyzing CO methanation at low temperature

doi:10.11949/0438-1157.20210778

Abstract

Abstract:

To improve the activity of Ni/SBA-16 catalyst in CO methanation at low temperature, Ni-Fe/SBA-16 bimetallic catalyst was prepared by introducing Fe promoter. The results of XPS, XRD, HRTEM and EDS-mapping characterization of the catalyst show that the addition of Fe forms a Ni₃Fe alloy with Ni, which reduces the size of the metal particles and reduces the average particle size of the metal particles from 60 nm to about 30 nm after reduction. Meanwhile, the H₂-TPR results showed that the formation of Ni₃Fe alloy strengthened the metal-support interaction, which would weaken the agglomeration of metal particles during the process of reduction and reaction. Finally, the analysis of CO-TPD and H₂-TPD indicated that the formation of Ni₃Fe alloy promoted the dissociation of reactant gas (CO and H₂), thus enhancing the catalytic activity of CO methanation catalyst at low temperature. As a result, the CO minimum complete conversion temperature was lowered to 250°C from 300°C with a CH₄ selectivity of 90% eventually at the condition of space velocity 150000 h^-1, P=0.1 MPa, V(H₂)∶V(CO)∶V(N₂)=3∶1∶1.

Key words: bimetalliccatalysts, carbon monoxide, methane, mesoscale, molecular sieves, nanoparticles

摘要：

为了提高Ni/SBA-16催化剂在低温下CO甲烷化中的活性，通过引入Fe助剂制备了Ni-Fe/SBA-16双金属催化剂。对催化剂进行XPS、XRD、HRTEM及EDS-mapping表征的结果表明，Fe的加入与Ni形成了Ni₃Fe合金，减小了金属颗粒尺寸，使得还原后金属颗粒平均粒径从60 nm降低到30 nm左右。同时H₂-TPR的结果表明，Ni₃Fe合金的形成增强了金属Ni与载体之间的相互作用，从而能够减弱Ni颗粒在还原过程及反应过程中的团聚。最后，由CO-TPD和H₂-TPD的测试结果可知，Ni₃Fe合金的形成促进了催化剂对反应气体CO和H₂的解离，从而提高了催化剂在低温下的CO甲烷化活性。当空速为150000 h^-1、压力为0.1 MPa、V(H₂)∶V(CO)∶V(N₂)=3∶1∶1时，CO最低完全转化温度可以从300°C降低到250°C，同时CH₄的选择性保持在90%。

关键词: 双金属催化剂, 一氧化碳, 甲烷, 介尺度, 分子筛, 纳米颗粒

CLC Number:

TQ 546.4

Wenli GAO, Zhong XIN. Research on promotion of Fe in Ni/SBA-16 catalyzing CO methanation at low temperature[J]. CIESC Journal, 2022, 73(1): 241-254.

高文莉, 辛忠. Fe对Ni/SBA-16催化CO低温甲烷化促进作用的研究[J]. 化工学报, 2022, 73(1): 241-254.

Figures/Tables 17

Fig.1 XPS patterns of catalysts

Fig.2 XRD patterns of catalysts

Fig.3 HRTEM and EDS-mapping images of Ni-2Fe/S16 catalyst

Fig.4 TEM images of support SBA-16

Fig.5 XRD patterns of the support SBA-16

Fig.6 Pore structures of support and catalysts tested by N2-physical adsorption-desorption

Table 1 Physical and chemical properties of support and catalyst

催化剂	Ni金属含量^①/ %	Fe金属含量^①/ %	比表面积^②/ (m²/g)	孔容^③/ (cm³/g)	金属分散度^④/ %	金属比表面积^④/ (m²/g)	金属颗粒尺寸^④/ nm
S16	—	—	938	0.74	—	—	—
Ni/S16	9.2	—	849	0.58	2.89	1.19	35.1
Ni-1Fe/S16	8.5	0.8	822	0.57	3.32	2.31	32.1
Ni-2Fe/S16	8.6	1.7	732	0.51	3.85	2.89	30.5
Ni-3Fe/S16	8.3	2.5	672	0.46	2.66	1.02	38.2

Table 2 The crystalline size of metal and its oxide

催化剂	还原前NiO平均颗粒尺寸/nm	还原后Ni平均颗粒尺寸/nm	反应后Ni平均颗粒尺寸/nm
Ni/S16	22.2	27.9	30.1
Ni-1Fe/S16	20.4	19.6	20.9
Ni-2Fe/S16	19.6	19.5	19.6
Ni-3Fe/S16	16.5	16.5	16.9

Fig.7 TEM images and the particle size distribution of catalysts after reduction

Fig.8 TEM images and the particle size distribution of catalysts after reaction

Fig.9 H2-TPR profiles of catalysts

Table 3 The peak analysis result of H2-TPR of catalysts

催化剂	低温峰面积比/%	高温峰面积比/%	500°C金属还原度/%
Ni/S16	62.4	37.6	96.9
Ni-1Fe/S16	49.2	50.8	71.3
Ni-2Fe/S16	44.0	56.0	68.0
Ni-3Fe/S16	60.6	39.4	81.0

Fig.10 Catalytic performance of Ni-xFe/S16 catalysts

Fig.11 CO methanation product distribution of Ni-xFe/S16 at different temperatures

Fig.12 Adsorption-dissociation profiles for reactant gas of catalysts

Table 4 The absorbed H2 and CO quantity of catalyst

催化剂	H₂
催化剂	吸附量/(cm³/g)	300°C 之前面积比/%	吸附量/(cm³/g)	300°C 之前面积比/%
Ni/S16	0.179	80.1	1.131	59.3
Ni-1Fe/S16	0.486	81.2	1.414	68.1
Ni-2Fe/S16	0.476	83.6	1.770	70.3
Ni-3Fe/S16	0.510	85.3	1.700	64.2

Fig.13 Schematic diagram of the structure-performance relationship of Ni-Fe/S16 catalyst

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