Preparation of a novel catalyst of La2O3-ZrO2-Ni /Al2O3 and its performance in syngas methanation

doi:10.16085/j.issn.1000-6613.2018-0787

Abstract

Abstract:

To overcome the limit of syngas methanation catalyst in thermal stability, activity or suitability, a novel catalyst, La₂O₃-ZrO₂-Ni/Al₂O₃, was prepared using La₂O₃ and ZrO₂ as multi-functional additive. Meanwhile, another catalyst of Cr₂O₃-Ni/Al₂O₃, was also prepared for reference. Then the microstructure of the catalyst was characterized by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The micropore parameters were determined by using N₂-adsorption (BET) method. And the theoretical equilibrium values of the four-stage methanation process adopted by a certain SNG plant were simulated by using Aspen Plus. Furthermore, the influence of pressure, space velocity and H₂O(g) content on the catalyst performance were investigated, and the 1000h life assessment was also conducted. The results show that La₂O₃-ZrO₂-Ni/Al₂O₃ is superior to Cr₂O₃-Ni/Al₂O₃ in thermal stability and temperature activity, which helps the conversion of CO and CO₂ approaching to the simulated equilibrium values. The active component, NiO, is well dispersed, with the particle sizes in the range of 7-10nm. The performance of La₂O₃-ZrO₂-Ni/Al₂O₃ is insensitive to the changes of pressure, space velocity or H₂O(g) content. Moreover, La₂O₃-ZrO₂-Ni/Al₂O₃ could preserve its high activity and stability after running for 1000h.

Key words: syngas, methanation, synthetic natural gas, catalyst, lanthanum oxide, zirconium dioxide, chromium sesguioxide, Ni/Al₂O₃

摘要：

针对常规合成气甲烷化催化剂高热结构稳定性差、活性低、适应性差等不足，本文创新地引用稀土金属氧化物La₂O₃复配过渡金属氧化物ZrO₂作为多功能复合助剂，利用反向沉淀法制备了新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni/Al₂O₃，同时制备催化剂Cr₂O₃-Ni/Al₂O₃作为参照组。采用X射线衍射（XRD）、透射电子显微镜（TEM）表征了催化剂的微观结构，并利用N₂吸附仪（BET）测量催化剂经高温水热处理前后的微孔结构参数，以考察催化剂的高热结构稳定性。结合国内某大型煤制天然气项目工艺特征和运行实践，应用Aspen Plus软件模拟了四段甲烷化工艺理论平衡值。基于自主固定床合成气甲烷化评价实验装置，考察了反应压力、空速和原料气H₂O(g)含量等因素对La₂O₃-ZrO₂-Ni/Al₂O₃催化性能的影响，并开展了1000h长周期寿命评价实验。结果表明，La₂O₃-ZrO₂-Ni/Al₂O₃比Cr₂O₃-Ni/Al₂O₃具有更优的高热结构稳定性；可使CO和CO₂反应达到或接近催化剂床层出口温度下的理论平衡状态，呈现显著的宽温活性；活性组分NiO晶粒尺寸介于7~10nm，分散度较高；对反应压力、空速和原料气H₂O(g)含量的变化不敏感，具有良好的操作弹性；1000h反应后仍能保持较高的活性和稳定性。

关键词: 合成气, 甲烷化, 合成天然气, 催化剂, La₂O₃, ZrO₂, Cr₂O₃, Ni/Al₂O₃

CLC Number:

O643

Chunqi LI. Preparation of a novel catalyst of La₂O₃-ZrO₂-Ni /Al₂O₃ and its performance in syngas methanation[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2776-2783.

李春启. 新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni /Al₂O₃的制备与性能[J]. 化工进展, 2019, 38(06): 2776-2783.

Figures/Tables 13

References 22

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催化剂	比表面积（S _BET） / m²·g^-1	孔容（V _p） / cm³·g^-1	平均孔径（D _p） / nm
催化剂A老化前	79.68	0.20	14.42
催化剂A老化后	40.25	0.13	14.45
催化剂B老化前	106.82	0.20	6.46
催化剂B老化后	37.78	0.13	15.43

催化剂	比表面积（S _BET） / m²·g^-1	孔容（V _p） / cm³·g^-1	平均孔径（D _p） / nm
催化剂A老化前	79.68	0.20	14.42
催化剂A老化后	40.25	0.13	14.45
催化剂B老化前	106.82	0.20	6.46
催化剂B老化后	37.78	0.13	15.43

反应工段	压力（P）/MPa	温度（T）/℃	组分含量(体积分数)/%
反应工段	压力（P）/MPa	温度（T）/℃	H₂	CO	CH₄	CO₂	H₂O
第一、二主甲烷化
入口	3.01	320.0	34.51	7.44	41.45	3.02	13.58
出口	2.99	620.0	20.08	1.61	53.01	3.92	21.39
第一补充甲烷化
入口	2.88	280.0	20.08	1.61	53.01	3.92	21.39
出口	2.82	445.0	6.84	0.00	61.67	1.71	29.78
第二补充甲烷化
入口	2.56	250.0	9.07	0.00	82.76	2.32	5.85
出口	2.50	324.0	1.41	0.00	88.12	0.40	10.07

反应工段	压力（P）/MPa	温度（T）/℃	组分含量(体积分数)/%
反应工段	压力（P）/MPa	温度（T）/℃	H₂	CO	CH₄	CO₂	H₂O
第一、二主甲烷化
入口	3.01	320.0	34.51	7.44	41.45	3.02	13.58
出口	2.99	620.0	20.08	1.61	53.01	3.92	21.39
第一补充甲烷化
入口	2.88	280.0	20.08	1.61	53.01	3.92	21.39
出口	2.82	445.0	6.84	0.00	61.67	1.71	29.78
第二补充甲烷化
入口	2.56	250.0	9.07	0.00	82.76	2.32	5.85
出口	2.50	324.0	1.41	0.00	88.12	0.40	10.07

反应工段	压力（P）/MPa	温度（T）/℃	催化剂A				催化剂B
反应工段	压力（P）/MPa	温度（T）/℃	H₂/%	CO/%	CH₄/%	CO₂/%	H₂/%	CO/%	CH₄/%	CO₂/%
主甲烷化出口	2.99	620.0	25.76	2.05	67.32	4.87	27.33	2.07	65.49	5.11
第一补充甲烷化出口	2.82	445.0	9.81	0.00	87.72	2.47	9.87	0.11	87.02	3.01
第二补充甲烷化出口	2.50	324.0	1.62	0.00	97.87	0.51	1.67	0.02	97.09	1.22

Preparation of a novel catalyst of La₂O₃-ZrO₂-Ni /Al₂O₃ and its performance in syngas methanation

新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni /Al₂O₃的制备与性能

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原料气H₂O(g)含量/%	反应器出口气体组成（干基）/%					转化率或选择性/%
原料气H₂O(g)含量/%	H₂	CO	CH₄	CO₂		CO转化率	CO₂转化率	CH₄选择性
6.49	20.36	1.32	74.62	3.70	88.32		16.56	107.33
12.96	23.28	1.32	70.87	4.53	87.80		-5.76	97.41
16.13	24.28	1.29	69.58	4.86	88.04		-14.25	93.63
19.43	26.14	1.34	67.19	5.33	87.14		-28.94	86.81

原料气H₂O(g) 含量/%	尾气组成（干基）/%
原料气H₂O(g) 含量/%	H₂	CO₂	CH₄
0.00	0.64	0.47	98.77
8.34	1.08	0.66	98.76
14.82	1.45	0.78	98.23

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