Fe对Ni/SBA-16催化CO低温甲烷化促进作用的研究

doi:10.11949/0438-1157.20210778

摘要/Abstract

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

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

中图分类号:

TQ 546.4

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.

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.

图/表 17

图1 催化剂的XPS谱图

Fig.1 XPS patterns of catalysts

图2 催化剂的XRD谱图

Fig.2 XRD patterns of catalysts

图3 Ni-2Fe/S16催化剂的HRTEM及EDS-mapping图

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

图4 载体SBA-16的TEM图

Fig.4 TEM images of support SBA-16

图5 载体SBA-16的XRD谱图

Fig.5 XRD patterns of the support SBA-16

图6 由N2物理吸附脱附仪测得的载体及催化剂的孔道结构

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

表1 载体及催化剂理化性质

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

表2 金属Ni及其氧化物颗粒平均尺寸

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

图7 还原后催化剂的TEM图及金属颗粒尺寸分布

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

图8 反应后催化剂的TEM图及金属颗粒尺寸分布

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

图9 催化剂的H2-TPR图

Fig.9 H2-TPR profiles of catalysts

表3 催化剂的H2-TPR 分峰分析结果

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

图10 Ni-xFe/S16催化剂的催化活性

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

图11 Ni-xFe/S16催化剂在不同温度下CO甲烷化产物分布

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

图12 催化剂对反应气体的吸附解离

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

表4 催化剂吸附的H2和CO量

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

图13 Ni-xFe/S16催化剂的构-效关系示意图

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

参考文献 52

1	Hussain I, Jalil A A, Fatah N A A, et al. A highly competitive system for CO methanation over an active metal-free fibrous silica mordenite viain situ ESR and FTIR studies[J]. Energy Conversion and Management, 2020, 211: 112754.
2	Han Y H, Quan Y H, Hao P P, et al. Highly anti-sintering and anti-coking ordered mesoporous silica carbide supported nickel catalyst for high temperature CO methanation[J]. Fuel, 2019, 257: 116006.
3	Liu Q, Zhong Z Y, Gu F N, et al. CO methanation on ordered mesoporous Ni-Cr-Al catalysts: effects of the catalyst structure and Cr promoter on the catalytic properties[J]. Journal of Catalysis, 2016, 337: 221-232.
4	Mills G A, Steffgen F W. Catalytic methanation[J]. Catalysis Reviews, 1974, 8(1): 159-210.
5	Meng F H, Li Z, Liu J, et al. Effect of promoter Ce on the structure and catalytic performance of Ni/Al₂O₃ catalyst for CO methanation in slurry-bed reactor[J]. Journal of Natural Gas Science and Engineering, 2015, 23: 250-258.
6	Zhang J Y, Xin Z, Meng X, et al. Synthesis, characterization and properties of anti-sintering nickel incorporated MCM-41 methanation catalysts[J]. Fuel, 2013, 109: 693-701.
7	Ren J, Li H D, Jin Y Y, et al. Silica/titania composite-supported Ni catalysts for CO methanation: effects of Ti species on the activity, anti-sintering, and anti-coking properties[J]. Applied Catalysis B: Environmental, 2017, 201: 561-572.
8	Zhang J Y, Xin Z, Meng X, et al. Effect of MoO₃ on structures and properties of Ni-SiO₂ methanation catalysts prepared by the hydrothermal synthesis method[J]. Industrial & Engineering Chemistry Research, 2013, 52(41): 14533-14544.
9	Lv Y H, Xin Z, Meng X, et al. Essential role of organic additives in preparation of efficient Ni/KIT-6 catalysts for CO methanation[J]. Applied Catalysis A: General, 2018, 558: 99-108.
10	Li S S, Gong D D, Tang H G, et al. Preparation of bimetallic Ni@Ru nanoparticles supported on SiO₂ and their catalytic performance for CO methanation[J]. Chemical Engineering Journal, 2018, 334: 2167-2178.
11	Lv Y H, Xin Z, Meng X, et al. Ni based catalyst supported on KIT-6 silica for CO methanation: confinement effect of three dimensional channel on NiO and Ni particles[J]. Microporous and Mesoporous Materials, 2018, 262: 89-97.
12	Bian Z C, Xin Z, Meng X, et al. Effect of citric acid on the synthesis of CO methanation catalysts with high activity and excellent stability[J]. Industrial & Engineering Chemistry Research, 2017, 56(9): 2383-2392.
13	Bai X B, Wang S, Sun T J, et al. Influence of operating conditions on carbon deposition over a Ni catalyst for the production of synthetic natural gas (SNG) from coal[J]. Catalysis Letters, 2014, 144(12): 2157-2166.
14	Rostrup-Nielsen J R, Pedersen K, Sehested J. High temperature methanation: sintering and structure sensitivity[J]. Applied Catalysis A: General, 2007, 330: 134-138.
15	Simonsen S B, Chorkendorff I, Dahl S, et al. Direct observations of oxygen-induced platinum nanoparticle ripening studied by in situ TEM[J]. Journal of the American Chemical Society, 2010, 132(23): 7968-7975.
16	Simonsen S B, Chorkendorff I, Dahl S, et al. Ostwald ripening in a Pt/SiO₂ model catalyst studied by in situ TEM[J]. Journal of Catalysis, 2011, 281(1): 147-155.
17	Trimm D L. Catalysts for the control of coking during steam reforming[J]. Catalysis Today, 1999, 49(1/2/3): 3-10.
18	Rönsch S, Schneider J, Matthischke S, et al. Review on methanation—from fundamentals to current projects[J]. Fuel, 2016, 166: 276-296.
19	Tao M, Xin Z, Meng X, et al. Impact of double-solvent impregnation on the Ni dispersion of Ni/SBA-15 catalysts and catalytic performance for the syngas methanation reaction[J]. RSC Advances, 2016, 6(42): 35875-35883.
20	Cao H X, Zhang J, Guo C L, et al. Modifying surface properties of KIT-6 zeolite with Ni and V for enhancing catalytic CO methanation[J]. Applied Surface Science, 2017, 426: 40-49.
21	Cao H X, Zhang J, Guo C L, et al. Highly dispersed Ni nanoparticles on 3D-mesoporous KIT-6 for CO methanation: effect of promoter species on catalytic performance[J]. Chinese Journal of Catalysis, 2017, 38(7): 1127-1137.
22	王昱涵, 白思雨, 崔丽杰, 等. Ni-Mo双金属催化剂的甲烷化性能与耐硫稳定性[J]. 化工学报, 2018, 69(5): 2063-2072.
	Wang Y H, Bai S Y, Cui L J, et al. Catalytic activity and sulfur-resistance stability of Ni-Mo-based catalysts for syngas methanation[J]. CIESC Journal, 2018, 69(5): 2063-2072.
23	Peng H G, Ying J W, Zhang J Y, et al. La-doped Pt/TiO₂ as an efficient catalyst for room temperature oxidation of low concentration HCHO[J]. Chinese Journal of Catalysis, 2017, 38(1): 39-47.
24	Liu Y, Sheng W, Hou Z G, et al. Homogeneous and highly dispersed Ni-Ru on a silica support as an effective CO methanation catalyst[J]. RSC Advances, 2018, 8(4): 2123-2131.
25	Konishcheva M V, Potemkin D I, Snytnikov P V, et al. The insights into chlorine doping effect on performance of ceria supported nickel catalysts for selective CO methanation[J]. Applied Catalysis B: Environmental, 2018, 221: 413-421.
26	Winter L R, Gomez E, Yan B H, et al. Tuning Ni-catalyzed CO₂ hydrogenation selectivity via Ni-ceria support interactions and Ni-Fe bimetallic formation[J]. Applied Catalysis B: Environmental, 2018, 224: 442-450.
27	Rombi E, Cutrufello M G, Atzori L, et al. CO methanation on Ni-Ce mixed oxides prepared by hard template method[J]. Applied Catalysis A: General, 2016, 515: 144-153.
28	Ai H M, Yang H Y, Liu Q, et al. ZrO₂-modified Ni/LaAl₁₁O₁₈ catalyst for CO methanation: effects of catalyst structure on catalytic performance[J]. Chinese Journal of Catalysis, 2018, 39(2): 297-308.
29	Guo C L, Wu Y Y, Qin H Y, et al. CO methanation over ZrO₂/Al₂O₃ supported Ni catalysts: a comprehensive study[J]. Fuel Processing Technology, 2014, 124: 61-69.
30	Liu Q, Gu F N, Gao J J, et al. Coking-resistant Ni-ZrO₂/Al₂O₃ catalyst for CO methanation[J]. Journal of Energy Chemistry, 2014, 23(6): 761-770.
31	Hong E, Bang S, Cho J H, et al. Reductive amination of isopropanol to monoisopropylamine over Ni-Fe/γ-Al₂O₃ catalysts: synergetic effect of Ni-Fe alloy formation[J]. Applied Catalysis A: General, 2017, 542: 146-153.
32	Kustov A L, Frey A M, Larsen K E, et al. CO methanation over supported bimetallic Ni-Fe catalysts: from computational studies towards catalyst optimization[J]. Applied Catalysis A: General, 2007, 320: 98-104.
33	Meng F H, Zhong P Z, Li Z, et al. Surface structure and catalytic performance of Ni-Fe catalyst for low-temperature CO hydrogenation[J]. Journal of Chemistry, 2014, 2014: 1-7.
34	Tian D Y, Liu Z H, Li D D, et al. Bimetallic Ni-Fe total-methanation catalyst for the production of substitute natural gas under high pressure[J]. Fuel, 2013, 104: 224-229.
35	Wang H, Zhang J F, Bai Y X, et al. NiO@SiO₂ core-shell catalyst for low-temperature methanation of syngas in slurry reactor[J]. Journal of Fuel Chemistry and Technology, 2016, 44(5): 548-556.
36	Zhang J F, Bai Y X, Zhang Q D, et al. Low-temperature methanation of syngas in slurry phase over Zr-doped Ni/γ-Al₂O₃ catalysts prepared using different methods[J]. Fuel, 2014, 132: 211-218.
37	Mesa M, Sierra L, Patarin J, et al. Morphology and porosity characteristics control of SBA-16 mesoporous silica. Effect of the triblock surfactant Pluronic F127 degradation during the synthesis[J]. Solid State Sciences, 2005, 7(8): 990-997.
38	Laosiripojana N, Assabumrungrat S. Catalytic steam reforming of ethanol over high surface area CeO₂: the role of CeO₂ as an internal pre-reforming catalyst[J]. Applied Catalysis B: Environmental, 2006, 66(1/2): 29-39.
39	Bian Z C, Meng X, Tao M, et al. Uniform Ni particles on amino-functionalized SBA-16 with excellent activity and stability for syngas methanation[J]. Journal of Molecular Catalysis A: Chemical, 2016, 417: 184-191.
40	Ren J, Mebrahtu C, Palkovits R. Ni-based catalysts supported on Mg-Al hydrotalcites with different morphologies for CO₂ methanation: exploring the effect of metal-support interaction[J]. Catalysis Science & Technology, 2020, 10(6): 1902-1913.
41	Parastaev A, Muravev V, Huertas Osta E, et al. Boosting CO₂ hydrogenation via size-dependent metal-support interactions in cobalt/ceria-based catalysts[J]. Nature Catalysis, 2020, 3(6): 526-533.
42	何璐铭, 辛忠, 高文莉, 等. 静电纺丝法制备高活性多孔Ni/SiO₂甲烷化催化剂[J]. 化工学报, 2020, 71(11): 5007-5015.
	He L M, Xin Z, Gao W L, et al. Highly efficient porous Ni/SiO₂ catalysts prepared by electrospinning method for CO methanation[J]. CIESC Journal, 2020, 71(11): 5007-5015.
43	Gao J J, Liu Q, Gu F N, et al. Recent advances in methanation catalysts for the production of synthetic natural gas[J]. RSC Advances, 2015, 5(29): 22759-22776.
44	Bligaard T, Nørskov J K, Dahl S, et al. The Brønsted-Evans-Polanyi relation and the volcano curve in heterogeneous catalysis[J]. Journal of Catalysis, 2004, 224(1): 206-217.
45	Liu Q, Gu F N, Lu X P, et al. Enhanced catalytic performances of Ni/Al₂O₃ catalyst via addition of V₂O₃ for CO methanation[J]. Applied Catalysis A: General, 2014, 488: 37-47.
46	Liu J, Li C M, Wang F, et al. Enhanced low-temperature activity of CO₂ methanation over highly-dispersed Ni/TiO₂ catalyst[J]. Catalysis Science & Technology, 2013, 3(10): 2627.
47	Eckle S, Anfang H G, Behm R J. Reaction intermediates and side products in the methanation of CO and CO₂ over supported Ru catalysts in H₂-rich reformate gases[J]. The Journal of Physical Chemistry C, 2011, 115(4): 1361-1367.
48	Cesteros Y, Salagre P, Medina F, et al. Effect of the alumina phase and its modification on Ni/Al₂O₃ catalysts for the hydrodechlorination of 1, 2, 4-trichlorobenzene[J]. Applied Catalysis B: Environmental, 1999, 22(2): 135-147.
49	Zhao B R, Liu P, Li S, et al. Bimetallic Ni-Co nanoparticles on SiO₂ as robust catalyst for CO methanation: effect of homogeneity of Ni-Co alloy[J]. Applied Catalysis B: Environmental, 2020, 278: 119307.
50	Han X X, Yang J Z, Guo H L, et al. Mechanism studies concerning carbon deposition effect of CO methanation on Ni-based catalyst through DFT and TPSR methods[J]. International Journal of Hydrogen Energy, 2016, 41(20): 8401-8411.
51	Andersson M P, Abild-Pedersen F, Remediakis I N, et al. Structure sensitivity of the methanation reaction: H₂-induced CO dissociation on nickel surfaces[J]. Journal of Catalysis, 2008, 255(1): 6-19.
52	Tanksale A, Beltramini J N, Dumesic J A, et al. Effect of Pt and Pd promoter on Ni supported catalysts—a TPR/TPO/TPD and microcalorimetry study[J]. Journal of Catalysis, 2008, 258(2): 366-377.

[1]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[2]	牛超, 沈胜强, 杨艳, 潘泊年, 李熠桥. 甲烷BOG喷射器流动过程计算与性能分析[J]. 化工学报, 2023, 74(7): 2858-2868.
[3]	刘晓洋, 喻健良, 侯玉洁, 闫兴清, 张振华, 吕先舒. 螺旋微通道对掺氢甲烷爆轰传播的影响[J]. 化工学报, 2023, 74(7): 3139-3148.
[4]	周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.
[5]	韩奎奎, 谭湘龙, 李金芝, 杨婷, 张春, 张永汾, 刘洪全, 于中伟, 顾学红. 四通道中空纤维MFI分子筛膜用于二甲苯异构体分离[J]. 化工学报, 2023, 74(6): 2468-2476.
[6]	陈巨辉, 张谦, 舒崚峰, 李丹, 徐鑫, 刘晓刚, 赵晨希, 曹希峰. 基于DEM方法的旋转流化床纳米颗粒流动特性研究[J]. 化工学报, 2023, 74(6): 2374-2381.
[7]	王荣, 王永洪, 张新儒, 李晋平. 6FDA型聚酰亚胺炭分子筛气体分离膜的构筑及其应用[J]. 化工学报, 2023, 74(4): 1433-1445.
[8]	王子健, 柯明, 李佳涵, 李舒婷, 孙巾茹, 童燕兵, 赵治平, 刘加英, 任璐. 短b轴ZSM-5分子筛制备方法及应用研究进展[J]. 化工学报, 2023, 74(4): 1457-1473.
[9]	胡晗, 杨亮, 李春晓, 刘道平. 天然烟浸滤液水合物法储甲烷动力学研究[J]. 化工学报, 2023, 74(3): 1313-1321.
[10]	彭晓婉, 郭笑楠, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8浆液法分离CH₄/N₂的双吸收-吸附塔工艺流程建模与模拟[J]. 化工学报, 2023, 74(2): 784-795.
[11]	白宇恩, 张彬瑞, 刘东阳, 赵亮, 高金森, 徐春明. ZSM-5分子筛酸性能和孔结构的协同作用对C₅烯烃催化裂解性能的影响[J]. 化工学报, 2023, 74(1): 438-448.
[12]	廖珊珊, 张少刚, 陶骏骏, 刘家豪, 汪金辉. 竖直射流火撞击障碍管道数值模拟分析[J]. 化工学报, 2022, 73(9): 4226-4234.
[13]	沈嘉辉, 王侃宏, 郁达伟, 胡大洲, 魏源送. 游离氨调理污泥厌氧消化优化产甲烷过程与强化有机物释放[J]. 化工学报, 2022, 73(9): 4147-4155.
[14]	刘振宇. 煤地下气化低效的化学反应工程根源：滞留层及通道中的传质与反应[J]. 化工学报, 2022, 73(8): 3299-3306.
[15]	艾承燚, 乔金硕, 王振华, 孙旺, 孙克宁. 原位析出纳米合金的PrBaFe₂O_6-_δ 基阳极构筑及其在固体碳燃料电池中的应用研究[J]. 化工学报, 2022, 73(8): 3708-3719.