Sn掺杂的In2O3催化CO2选择性加氢制甲醇

doi:10.11949/0438-1157.20230442

摘要/Abstract

摘要：

选择性加氢制甲醇是CO₂资源化利用最主要的方式之一，因此十分需要开发高效的合成甲醇催化剂。本研究采用共沉淀法在In₂O₃中掺杂Sn来调控In₂O₃的还原能力和表面氧空位浓度，以提升In₂O₃催化剂在CO₂加氢制甲醇中的催化性能。通过XRD、TEM、H₂-TPR、H₂-D₂-TPSR、Raman、XPS、CO₂-TPD等表征手段，研究了Sn助剂对催化剂结构和表面化学性质的影响；并通过高压固定床装置测试了催化剂的催化性能。结果表明，Sn在In₂O₃中高度分散并倾向于在表面富集，与In₂O₃形成Sn—O—In结构，促进了表面氧空位的生成，且能抑制In₂O₃的过度还原，从而使得Sn-In₂O₃催化剂表现出更高的甲醇选择性和产率。在300℃、3 MPa、空速为15000 ml·g^-1·h^-1的反应条件下，Sn/In摩尔比为0.5%的Sn-In₂O₃催化剂具有最优的催化性能，此时CO₂转化率为6.2%，甲醇选择性为70.4%，当Sn含量进一步增加时，CO₂转化率会略有下降，而甲醇选择性提升至80.8%。

关键词: 催化剂, 二氧化碳, 加氢, In₂O₃, Sn掺杂, 氧空位, 甲醇合成

Abstract:

Selective hydrogenation of CO₂ to methanol is one of the most important ways of resource utilization of CO₂, so it is very necessary to develop efficient methanol synthesis catalysts. In this study, the Sn promoter has been incorporated into In₂O₃ to modify its reducibility and the surface oxygen vacancy, in order to optimize the catalytic performance of In₂O₃ catalyst for CO₂ hydrogenation to methanol. Several characterizations including XRD, TEM, H₂-TPR, H₂-D₂-TPSR, Raman, XPS, and CO₂-TPD were conducted to reveal the effect of Sn promoter on the structure and chemistry of the catalysts. The activity tests were performed in a high pressure fixed-bed reactor to study the catalytic performance. The results showed that the Sn atoms were highly dispersed in In₂O₃ and tended to accumulate on the surface through forming Sn—O—In structure, which promotes the formation of surface oxygen vacancy, and can inhibit the excessive reduction of In₂O₃. As a result, the Sn promoted In₂O₃ catalysts exhibited higher methanol selectivity and productivity. The Sn-In₂O₃ catalyst with a Sn/In molar ratio of 0.5% possessed the optimized catalytic performance, which showed a CO₂ conversion of 6.2% and methanol selectivity of 70.4% at the reaction conditions of 300℃ and 3 MPa with GHSV of 15000 ml·g^-1·h^-1. With further increment of Sn content, the CO₂ conversion would slightly decrease, while the methanol selectivity would increase to 80.8%, significantly higher than that of 55.4% on the pure In₂O₃ catalyst.

Key words: catalyst, CO₂, hydrogenation, In₂O₃, Sn incorporation, oxygen vacancy, methanol production

中图分类号:

TQ 546.4

杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.

Feifei YANG, Shixi ZHAO, Wei ZHOU, Zhonghai NI. Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol[J]. CIESC Journal, 2023, 74(8): 3366-3374.

图/表 11

图1 不同催化剂的N2吸/脱附曲线

Fig.1 The N2 adsorption-desorption isotherms of different catalysts

图2 不同催化剂的XRD谱图(后缀-R表示反应后的催化剂)

Fig.2 XRD patterns of different catalysts

图3 In2O3、2Sn-In2O3的TEM图及2Sn-In2O3的EDS mapping图（后缀-R表示反应后的催化剂）

Fig.3 TEM image of In2O3 and 2Sn-In2O3 and EDS mapping of 2Sn-In2O3 catalyst

图4 不同催化剂的H2-TPR曲线

Fig.4 H2-TPR profile of different catalysts

图5 In2O3和0.5Sn-In2O3催化剂H2-D2-TPSR测试中HD生成曲线（m/z=3）

Fig.5 HD formation profile during H2-D2-TPSR experiment over In2O3 and 0.5Sn-In2O3 catalysts (m/z=3)

图6 不同催化剂的Raman谱图

Fig.6 Raman spectra of different catalysts

图7 不同催化剂中O 1s、In 3d、Sn 3d的XPS谱图

Fig.7 XPS spectra of O 1s, In 3d, Sn 3d for different catalysts

图8 不同催化剂的CO2-TPD图

Fig.8 CO2-TPD profile of different catalysts

图9 Sn含量对CO2转化率、产物选择性以及甲醇的时空收率的影响

Fig.9 The effect of Sn content on CO2 conversion, product selectivity and the space time yield (STY) of methanol (reaction conditions: T=300℃, P=3 MPa, GHSV=15000 ml·g-1·h-1, TOS=1 h)

表1 Sn-In2O3催化剂与文献报道的In2O3基催化剂用于CO2加氢制甲醇的比较

Table 1 Comparison of Sn-In2O3 with the reported In2O3 based catalysts for CO2 hydrogenation to methanol

Catalyst	Reaction condition		GHSV/ (ml·g^-1·h^-1)	CO₂ conversion/%	S_Methanol/%	STY/ (mmol·g^-1·h^-1)	Ref.
Catalyst	T/℃	P /MPa	GHSV/ (ml·g^-1·h^-1)	CO₂ conversion/%	S_Methanol/%	STY/ (mmol·g^-1·h^-1)	Ref.
In₂O₃	300	3	15000	5.9	55.4	5.0	this work
0.5Sn-In₂O₃	300	3	15000	6.2	70.4	6.9	this work
2Sn-In₂O₃	300	3	15000	4.5	80.8	5.6	this work
In₂O₃	300	4	24000	~5	~60	7.4	[25]
Pt-In₂O₃	300	4	24000	~9	~67	14.8	[25]
In₂O₃	300	5	21000	8	71	10	[20]
Ir-In₂O₃	300	5	21000	17.7	70	24.1	[20]
Pd-In₂O₃	300	5	21000	21	71	27.8	[22]
Au-In₂O₃	300	5	21000	11.7	67.8	14.7	[26]
In₂O₃	300	5	21000	9	61	10.3	[27]
Pt/In₂O₃	300	5	21000	17.5	53	16.6	[27]

图10 不同催化剂中CO2的转化率随运行时间的变化

Fig.10 CO2 conversion as a function of TOS over different catalysts (reaction conditions: T=300℃, P=3 MPa, GHSV=15000 ml·g-1·h-1)

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Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇

Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol

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