V2O5/Ti-Ce-PILC在H2S选择性催化氧化过程中的催化性能

董雁春; 李洋; 张金刚; 代正华; 于广锁; 王辅臣

V₂O₅/Ti-Ce-PILC在H₂S选择性催化氧化过程中的催化性能

董雁春^{1, 2},
李洋^{1, 2},
张金刚^{1, 2},
代正华^{1, 2},
于广锁^{1, 2},
王辅臣^{1, 2, ,}

1.
华东理工大学煤气化及能源化工教育部重点实验室, 上海 200237
2.
煤基能源化工协同创新中心, 上海 200237

基金项目:

国家自然科学基金 21376079

详细信息

通讯作者:
王辅臣, E-mail:wfch@ecust.edu.cn

中图分类号: TQ541
计量
- 文章访问数: 58
- HTML全文浏览量: 24
- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2016-05-06
- 修回日期: 2016-07-26
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

Catalytic performance of V₂O₅/Ti-Ce-PILC in the selective oxidation of H₂S

DONG Yan-chun^{1, 2},
LI Yang^{1, 2},
ZHANG Jin-gang^{1, 2},
DAI Zheng-hua^{1, 2},
YU Guang-suo^{1, 2},
WANG Fu-chen^{1, 2
, ,}

1.
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, East China University of Science & Technology, Shanghai 200237, China
2.
Collaborative Innovation Center of Chemical Technology for Coal Based Energy, Shanghai 200237, China

Funds:

the National Nature Science Foundation of China 21376079

摘要

摘要: 合成了TiO₂-CeO₂柱撑黏土负载V₂O₅催化剂，通过XRD、氮气吸附脱附、TG、FT-IR、H₂-TPR、NH₃-TPD、XPS等方法对其物理化学性质进行了表征，研究了该催化剂在H₂S选择性催化氧化反应中的活性。结果表明，负载5%V₂O₅的TiO₂-CeO₂柱撑黏土在180℃下催化效果最好，且尾气中不含SO₂。V₂O₅、TiO₂和CeO₂之间的相互作用提高了催化剂的活性，CeO₂提高了催化剂的热稳定性，同时提供大量晶格氧，加强了V₂O₅的氧化还原作用，降低了反应温度；TiO₂加强了VO_x和CeO_x的再氧化，降低了硫酸盐的覆盖率，从而降低了催化剂的失活速率。
- 柱撑黏土 /
- TiO₂ /
- CeO₂ /
- H₂S /
- 催化氧化
Abstract: A series of V₂O₅ doped Ti-Ce-pillared clays (V₂O₅/Ti-Ce-PILC) were prepared and characterized by XRD, nitrogen physisorption, FT-IR, XPS, H₂-TPR, TG and NH₃-TPD. The catalytic performance of V₂O₅/Ti-Ce-PILC in the selective oxidation of H₂S was investigated in a fixed bed reactor. The results illustrated that 5%V₂O₅ doped Ti-Ce-pillared clays performs well at 180℃ in the selective oxidation of H₂S, which can be ascribed to the interaction among V₂O₅, TiO₂ and CeO₂. CeO₂ can enhance the catalyst thermostability and supply more lattice oxygen, which is of benefits to the redox of V₂O₅ and the decrease of reaction temperature. Meanwhile, the addition of TiO₂ may promote the reoxidation of VO_x and CeO_x and reduce the sulfate coverage, which can then postpone the catalyst deactivation.
- pillared clays /
- TiO₂ /
- CeO₂ /
- H₂S /
- catalytic oxidation

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图 1 硫化氢催化过程流程示意图

Figure 1 Schematic diagram of the apparatus for selective catalytic oxidation of H₂S

1: H₂S; 2: O₂; 3: N₂; 4: mass flow controllers; 5: commingler; 6: tube furnace; 7: fixed bed reactor; 8: thermocouple; 9: condenser; 10: gas chromatogragh; 11: computer; 12: NaOH wash bottle

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图 2 不同PILC (柱撑黏土) 催化剂的XRD谱图

Figure 2 XRD patterns of laponite and PILC catalysts

a: laponite; b: Ti-PILC; c: V₂O₅/Ti-PILC; d: Ce-PILC; e: V₂O₅/Ce-PILC; f: Ti-Ce-PICL; g: V₂O₅/Ti-Ce-PILC

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图 3 Laponite及PILC催化剂的热重曲线

Figure 3 TG patterns of laponite and PILC catalysts

a: laponite; b: V₂O₅/Ti-PILC; c: V₂O₅/Ce-PILC; d: V₂O₅/Ti-Ce-PILC

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图 4 Laponite及PILC催化剂的FT-IR谱图

Figure 4 FT-IR patterns of laponite and PILC catalysts

a: laponite; b: Ti-PILC; c: Ce-PILC; d: Ti-Ce-PICL; e: V₂O₅/Ti-PILC; f: V₂O₅/Ce-PILC; g: V₂O₅/Ti-Ce-PILC

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图 5 PILC催化剂的H₂-TPR谱图

Figure 5 H₂-TPR patterns of PILC catalysts

(a) a: Ti-PILC; b: Ce-PILC; c: Ti-Ce-PILC; (b) a: V₂O₅/Ti-PILC; b: V₂O₅/Ce-PILC; c: V₂O₅/Ti-Ce-PILC

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图 6 PILC催化剂的NH₃-TPD谱图

Figure 6 NH₃-TPD patterns of PILC catalysts

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图 7 催化剂的H₂S转化率随温度的变化

Figure 7 H₂S conversion for selective oxidation over the PILC catalysts

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图 8 催化剂的稳定性能

Figure 8 Stability of the PILC catalysts in the selective oxidation of H₂S

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图 9 反应前后V₂O₅/Ti-Ce-PILC、V₂O₅/Ce-PILC催化剂的XPS谱图

Figure 9 Experimental and fitted XPS spectra of fresh and used V₂O₅/Ti-Ce-PILC, V₂O₅/Ce-PILC catalysts

(a): Ce 3d; (b): V 2p; (c): O 1s; (d): S 2p

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图 10 180 ℃下V₂O₅/Ti-Ce-PILC催化剂五次失活再生的H₂S转化率

Figure 10 Conversion of H₂S for the selective oxidation over V₂O₅/Ti-Ce-PILC catalyst at 180 ℃ in 5 cycles with successive regeneration

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表 1 催化剂的比表面积和孔结构

Table 1 BET specific surface areas total pore volume average pore diameter of various catalysts

Sample	A_BET/(m²·g^-1)	v_p/(cm³·g^-1)	d_p/nm
Laponite	145	0.18	2.93
Ti-PILC	208	0.35	7.09
Ce-PILC	306	0.48	7.50
Ti-Ce-PILC	247	0.46	10.13
V₂O₅/Ti-PILC	172	0.25	5.19
V₂O₅/Ce-PILC	251	0.48	5.08
V₂O₅/Ti-Ce-PILC	179	0.27	6.77

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表 2 样品的XPS分析

Table 2 XPS analysis data of various catalysts

Catalyst	Relative content ratio
Catalyst	Ce³⁺/Ce⁴⁺	V⁴⁺/V⁵⁺	lattice oxygen/adsorbed oxygen	SO₄^2-/S_n
V₂O₅/Ti-Ce-PILC (fresh)	0.302	0.000	0.696	-
V₂O₅/Ti-Ce-PILC (used)	0.325	0.674	0.631	1.223
V₂O₅/Ce-PILC (fresh)	0.262	0.000	0.508	-
V₂O₅/Ce-PILC (used)	0.412	0.754	0.286	2.327

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表 3 样品的XPS结合能

Table 3 XPS binding energy of various catalysts

Element	Binding energy E/eV
Element	V₂O₅/Ti-Ce-PILC (fresh)	V₂O₅/Ti-Ce-PILC (used)	V₂O₅/Ce-PILC (fresh)	V₂O₅/Ce-PILC (used)
Ce⁴⁺ 3d_5/2	883.2	882.2	882.7	882.7
Ce⁴⁺ 3d_3/2	901.3	900.3	900.8	900.8
Ce⁴⁺ 3d_5/2	898.9	897.8	898.5	898.4
Ce⁴⁺ 3d_3/2	917.0	915.8	916.6	916.5
Ce⁴⁺ 3d_5/2	888.1	888.1	887.9	889.0
Ce⁴⁺ 3d_3/2	906.2	906.2	906.0	907.1
Ce³⁺ 3d_5/2	886.0	885.4	885.8	886.0
Ce³⁺ 3d_3/2	904.1	903.5	903.9	904.0
Ti⁴⁺ 2p_5/2	458.2	458.7	-	-
Ti⁴⁺ 2p_3/2	464.0	464.3	-	-
V⁵⁺ 2p_3/2	517.8	518.0	518.1	518.2
V⁴⁺ 2p_5/2	-	517.0	-	517.0
Adsorbed oxygen	531.4	531.8	531.2	531.5
Lattice oxygen	529.3	529.5	529.4	529.0
S_n	-	162.9	-	163.2
SO₄^2-	-	169.1	-	168.5

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