催化甲烷重整工艺的研究进展

doi:10.11949/0438-1157.20240625

摘要/Abstract

摘要：

天然气储量丰富，是优质的清洁能源，甲烷作为其主要成分，通常经由重整工艺来制备。而重整过程中由积炭烧结等引起的催化剂失活问题是阻碍该工艺大规模工业化发展的关键因素。基于铁基催化剂，从催化剂活性组分、载体、助剂以及制备方法等角度综述了甲烷裂解重整催化剂性能的研究进展。基于Ni-Fe双金属催化剂综述了甲烷蒸汽重整及二氧化碳重整催化剂性能的研究进展。阐述了催化剂的失活原因以及提高重整催化剂性能的方法。为了促进重整工艺的工业应用，未来应深度探讨铁基催化剂的积炭机理，选取合适的载体及助剂来优化铁基催化剂的性能。

关键词: 甲烷重整, 催化剂, 铁基催化, 活性, 失活

Abstract:

Natural gas is abundant, and methane is the main ingredient, which is usually used through reforming to produce high-quality clean energy. However, the catalyst deactivation caused by carbon deposition and sintering in the reforming process is a key factor hindering the large-scale industrial development of this process. Based on iron-based catalysts, the research progress on the performance of methane cracking reforming catalysts was reviewed from the perspectives of catalyst active components, supports, additives and preparation methods. Based on Ni-Fe bimetallic catalysts, the research progress on the performance of methane steam reforming and carbon dioxide reforming catalysts was reviewed. The causes of catalyst deactivation and the methods to improve the performance of reforming catalysts are described. In order to promote the industrial application of the reforming process, the carbon deposition mechanism of iron-based catalysts should be deeply explored in the future, and appropriate carriers and additives should be selected to optimize the performance of iron-based catalysts.

Key words: methane reforming, catalyst, iron-based catalysis, activity, deactivation

中图分类号:

TF 554

石美琳, 赵连达, 邓行健, 王静松, 左海滨, 薛庆国. 催化甲烷重整工艺的研究进展[J]. 化工学报, 2024, 75(S1): 25-39.

Meilin SHI, Lianda ZHAO, Xingjian DENG, Jingsong WANG, Haibin ZUO, Qingguo XUE. Research progress on catalytic methane reforming process[J]. CIESC Journal, 2024, 75(S1): 25-39.

图/表 16

图1 甲烷的转化方式及用途

Fig.1 Conversion mode and use of methane

表1 甲烷重整工艺

Table 1 Methane reforming process

甲烷重整工艺	反应方程式	H₂/CO	优点	缺点
裂解重整	CH₄ $\overset{}{̿}$ C+2H₂	—	不产生污染气体CO₂的同时产生高附加值的碳产品，绿色经济	碳的形成和沉积造成催化剂失活
蒸汽重整	CH₄+H₂O $\overset{}{̿}$ 3H₂+CO	3∶1	可以产生更高浓度的氢，运行效率高，产业成熟度高	外部热交换装置的额外费用高
干重整	CH₄+CO₂ $\overset{}{̿}$ 2CO+2H₂	1∶1	同时使用了两种温室气体	高温条件下催化剂易积炭烧结
部分氧化重整	CH₄+1/2O₂ $\overset{}{̿}$ CO+2H₂	2∶1	对硫杂质有更高的耐受性，能耗少，经济	纯氧成本高，气体混合物可能会发生爆炸

表1 甲烷重整工艺

Table 1 Methane reforming process

甲烷重整工艺	反应方程式	H₂/CO	优点	缺点
裂解重整	CH₄ $\overset{}{̿}$ C+2H₂	—	不产生污染气体CO₂的同时产生高附加值的碳产品，绿色经济	碳的形成和沉积造成催化剂失活
蒸汽重整	CH₄+H₂O $\overset{}{̿}$ 3H₂+CO	3∶1	可以产生更高浓度的氢，运行效率高，产业成熟度高	外部热交换装置的额外费用高
干重整	CH₄+CO₂ $\overset{}{̿}$ 2CO+2H₂	1∶1	同时使用了两种温室气体	高温条件下催化剂易积炭烧结
部分氧化重整	CH₄+1/2O₂ $\overset{}{̿}$ CO+2H₂	2∶1	对硫杂质有更高的耐受性，能耗少，经济	纯氧成本高，气体混合物可能会发生爆炸

表2 甲烷裂解工艺催化材料分类

Table 2 Classification of catalytic materials for methane cracking process

项目	分类	作用
活性组分	贵金属类：Pt、Ru、Rh等非贵金属类：Ni、Fe、Co等碳基：石墨、活性炭、金刚石等	催化甲烷裂解，能够解离活化甲烷分子，具有活化O—O、H—O键等的能力
载体	Al₂O₃、SiO₂、MgO、CeO、ZrO₂、钙钛矿、介孔材料等	起到骨架的作用，可与活性组分相互作用，负载活性组分
助剂	MgO、CaO、CeO₂、La₂O₃等	提高催化剂活性、抗积炭抗烧结等能力
制备方法	溶胶-凝胶法、共沉淀法、浸渍法等	制备合成催化剂

表3 Ermakova等［10］的研究结果

Table 3 Research results of Ermakova et al［10］

活性组分	载体	析碳量/g	氢体积/cm³
Fe	ZrO₂	13.5	50.4
Fe	Al₂O₃	14	52.3
Fe	TiO₂	17.4	64.9
Fe	SiO₂	45	168
Fe	—	16.5	61.6

表4 催化剂制备方法对甲烷分解中测试的Fe基催化剂的催化性能的影响［18］

Table 4 Influence of catalyst preparation method on catalytic performance of Fe catalyst tested in methane decomposition［18］

催化剂	制备方法	甲烷转化率%	催化剂寿命/h	析碳量/g
Fe-Al₂O₃	浸渍法[Fe(NO₃)₃]	—	2	1.1
Fe-SiO₂	浸渍法[Fe(NO₃)₃]	—	2	0.7
Fe-Al₂O₃	共沉淀法（NH₄OH）	4	23	26.5
Fe-Al₂O₃	共沉淀法（NaOH）	6	6	3.3
Fe-Al₂O₃	共沉淀法（Na₂CO₃）	4	6	2.3

图2 蒸汽重整工艺图[20]

Fig.2 Steam reforming process diagram[20]

图3 镍铁改性方解石机理图[27]

Fig.3 Mechanism diagram of nickel-iron modified calcite[27]

图4 CO2/CH4体系在1 atm (a)和10 atm (b)下的平衡组分[33]（1 atm=101.325 kPa）

Fig.4 Equilibrium components of the CO2/CH4 system at 1 atm (a) and 10 atm (b)[33]

图5 Fe-Ni催化剂的TEM图像[44]

Fig.5 TEM images of Fe-Ni catalyst[44]

图6 C-O-H2三元相图在直接还原工艺中的应用[53]

Fig.6 Application of C-O-H2 ternary phase diagram in direct reduction process[53]

表5 催化剂失活现象部分相关研究

Table 5 Partial studies on catalyst deactivation

工艺	催化剂	失活原因	文献
催化裂解重整	Ni-SiO₂	活性中心组分Ni烧结、积炭	[54]
催化裂解重整	Fe-Al₂O₃	积炭	[18]
蒸汽重整	Fe	Fe氧化	[23]
蒸汽重整	Ni-Ce/Al	活性中心组分Ni烧结	[55]
蒸汽重整	Ni/Ni-Ru	活性中心组分Ni烧结	[56]
蒸汽重整	Ni-Ru/CeO₂-Al₂O₃	硫中毒	[57]
蒸汽重整	Pt/CeO₂-La₂O₃-Al₂O₃	活性中心组分Pt烧结	[58]
干重整	Fe-Al₂O₃	积炭	[36]
干重整	Ni-Fe	积炭	[59]
干重整	Ni-SiO₂/TiO₂/MgO	活性中心组分Ni烧结、积炭	[60]
干重整	Ni	活性中心组分Ni烧结	[37]
干重整	Ni/MgO	Ni氧化	[61]
干重整	Ni-Co/TiO₂	Co氧化	[62]
干重整	Co/γ-Al₂O₃	Co氧化	[63]

图7 ∆G⊝-T 曲线

Fig.7 ∆G⊝ -T curve

图8 C-H-O三元相图（1atm)

Fig.8 C-H-O ternary phase diagram (1atm)

图9 碳化铁颗粒上碳丝成核和生长阶段示意图

Fig.9 Schematic diagram of nucleation and growth stages of carbon filaments on iron carbide particles

图10 铁催化剂上的甲烷裂解机理模型[67]

Fig.10 Mechanism model of methane pyrolysis on iron catalyst[67]

图11 甲烷和二氧化碳活化路径

Fig.11 Activation pathways of methane and carbon dioxide

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