Pt涂層蜂窩金屬和Ce改性Fe<sub>2</sub>O<sub>3</sub>催化CO的性能對比

周昊; 成毅; 周明熙; 倪玉國

doi:10.13374/j.issn2095-9389.2019.04.08.005

Pt涂層蜂窩金屬和Ce改性Fe₂O₃催化CO的性能對比

doi: 10.13374/j.issn2095-9389.2019.04.08.005

浙江大學能源清潔利用國家重點實驗室, 杭州 310027

基金項目: 國家杰出青年基金資助項目(51825605)

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通訊作者:
E-mail: zhouhao@zju.edu.cn

中圖分類號: X511.0
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出版歷程
- 收稿日期: 2019-04-08
- 刊出日期: 2020-01-01

Analysis of CO catalytic oxidation by Pt-loading catalyst and Ce-doped Fe₂O₃

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

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Corresponding author: E-mail: zhouhao@zju.edu.cn

摘要

摘要: 鐵礦石燒結煙氣中含有較高濃度的CO（體積分數0.5%～2%），因此對其進行CO脫除意義重大。為了探究不同類型催化劑的催化效果，采用浸漬法制備了Pt涂層蜂窩金屬催化劑和鐵鈰氧化物催化劑，并通過X射線熒光光譜分析（XRF）對其組分含量進行了分析。二者在模擬燒結煙氣中進行CO脫除性能的對比實驗，活性測試表明，不同CO初始體積分數、煙氣溫度以及水汽含量對CO催化氧化的脫除效率影響較大。當模擬煙氣中不含水汽的時候，二者在180 ℃及更高溫度下對CO的脫除效率均能達到60%以上。反應溫度為180 ℃，水汽體積分數為11.7%時，Pt負載型催化劑中的CO轉化率為63.9%，而該條件下Ce改性Fe₂O₃催化劑的CO轉化率僅為34.9%。當溫度在180～300 ℃范圍內，Pt負載型催化劑具有較好的抗水性，且繼續升高溫度，水汽體積分數增加對催化劑效率的負面影響更顯著。如水汽體積分數從0增加到27.1%時，與180 ℃時的催化效率相比，Pt負載型催化劑在240 ℃時的催化效率由73.9%降至62.3%，降幅遠遠增大。另外，對這兩種催化劑進行了抗硫性測試。當水汽體積分數為0時，Ce改性Fe₂O₃催化劑抗硫性更佳，但當SO₂和水汽同時存在的情況下，Pt負載型催化劑具有更好的抗硫性。因此，在實際燒結中建議采取高效的脫硫措施并布置脫水層以減少其對于催化劑的負面影響。
- 催化劑 /
- 氧化 /
- 還原 /
- 一氧化碳 /
- 鐵礦石燒結 /
- 濕度
Abstract: The iron ore sintering flue gas contains a relatively high CO concentration (volume fraction of 0.5%?2%); therefore, it is of great significance to remove CO. To study the catalytic effect of different catalysts, typical Pt-supported catalyst and Ce-doped Fe₂O₃ catalyst were prepared by impregnation, and their components were analyzed by X-ray fluorescence. The activity results show that different initial CO concentrations, flue gas temperature, and water vapor volume fraction have a great influence on the removal efficiency of CO catalytic oxidation. When there is no water vapor in the flue gas, the CO removal efficiency of the two catalysts is over 60%. When the reaction temperature is 180 ℃ and the water vapor volume fraction is 11.7%, the CO conversion efficiency of the Pt-supported catalyst is 63.9%, but the CO conversion efficiency of the Ce-doped Fe₂O₃ catalyst is only about 34.9%. Furthermore, the results show that the Pt-supported catalyst has a better water resistance in the range of 180?300 ℃. If the reaction temperature is higher, the increase in water vapor volume will have a more negative impact on the catalytic efficiency of both catalysts. For example, when the volume fraction of water vapor increases from 0 to 27.1%, the catalytic efficiency of the Pt-supported catalyst drops from 73.9% to 62.3%, which decreases much more compared to the case of 180 ℃. In addition, the sulfur resistance of the two catalysts was also tested. The Ce-doped Fe₂O₃ catalyst is more resistant to SO₂, when there is no water vapor. However, when SO₂ and water vapor exist at the same time, the Pt-supported catalyst has better sulfur resistance. Therefore, during the actual sintering process, it is recommended to adopt efficient desulfurization measures and arrange the water absorption layer in order to reduce the negative impacts on catalysts.
- catalyst /
- oxidation /
- reduction /
- carbon monoxide /
- iron ore sinter /
- humidity

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圖 1 模擬燒結尾氣CO脫除實驗裝置圖

Figure 1. Schematic diagram of the experimental rig for CO removal

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圖 2 不同初始CO體積分數下催化劑的脫除結果。（a） Pt蜂窩金屬催化劑；（b） Ce改性的Fe₂O₃；（c）兩者脫除效率

Figure 2. Removal results of the catalyst at different initial CO concentrations: (a) Pt catalyst; (b) Ce?modified Fe₂O₃; (c) removal efficiency

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圖 3 催化劑在不同溫度下的脫除結果。（a） Pt蜂窩金屬催化劑；（b） Ce改性的Fe₂O₃；（c）兩者脫除效率

Figure 3. Removal results of the catalyst at different temperatures: (a) Pt catalyst; (b) Ce?modified Fe₂O₃; (c) removal efficiency

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圖 4 Pt蜂窩金屬催化劑在不同水汽體積分數下的CO脫除性能。（a） 180 ℃；（b） 240 ℃

Figure 4. Removal results of Pt catalyst under different water vapor volume fractions: (a) 180 ℃; (b) 240 ℃

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圖 5 Ce改性的Fe₂O₃催化劑在不同水汽體積分數下的CO脫除性能。（a） 180 ℃；（b） 240 ℃

Figure 5. Removal results of Fe₂O₃?CeO₂ catalyst under different water vapor volume fractions: (a) 180 ℃; (b) 240 ℃

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圖 6 不同水汽體積分數下兩種催化劑不同溫度的脫除效率

Figure 6. Removal efficiency of two catalysts under different water vapor volume fractions

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圖 7 兩種催化劑抗硫性測試（CO初始體積分數4.7 × 10^?3，溫度為180 ℃）

Figure 7. Sulfur resistance tests of two catalysts（the initial volume fraction of CO is 4.7×10^?3, temperature is 180 ℃）

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表 1 催化劑性能測試試驗工況表

Table 1. Test conditions of catalysts

工況	反應溫度/℃	水汽體積分數/%	近似初始CO體積分數/10^?3
1	180	0	2
2	180	0	3
3	180	0	5
4	180	0	7.5
5	120	0	4.5
6	180	0	4.5
7	240	0	4.5
8	300	0	4.5
9	180	11.7	4.5
10	180	19.9	4.5
11	180	27.1	4.5
12	240	11.7	4.5
13	240	19.9	4.5
14	240	27.1	4.5

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表 2 兩種催化劑的比表面積測試結果

Table 2. BET test results of two catalysts

樣品	比表面積/（m²·g^?1）
Pt/Al₂O₃涂層蜂窩金屬型催化劑	50.9
Ce改性Fe₂O₃?Al₂O₃催化劑	44.7

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表 3 Pt/Al₂O₃涂層蜂窩金屬型催化劑XRF分析結果（質量分數）

Table 3. XRF test results of Pt/Al₂O₃ catalyst %

Al	Fe	Cr	Ni	Pt	Si	Gd	Mn	Mg	Ca
36.99	36.69	12.98	2.07	0.448	0.26	0.24	0.15	0.0684	0.0592

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表 4 Ce改性Fe₂O₃催化劑XRF分析結果（質量分數）

Table 4. XRF test results of Ce-doped Fe₂O₃ catalyst %

Al₂O₃	Fe₂O₃	CeO₂	NiO	F	SiO₂	PtO₂	Gd₂O₃	MnO	MgO
48.96	29.21	7.28	1.39	0.5	0.369	0.272	0.117	0.112	0.0805

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