氧化还原沉淀法制备Mn-Ce-Co-O<sub><i>x</i></sub>/PPS滤料及其低温SCR活性

付彬彬; 郑玉婴; 陈健; 邹海强; 郑伟杰; 陈雪红

氧化还原沉淀法制备Mn-Ce-Co-O_x/PPS滤料及其低温SCR活性

福州大学材料科学与工程学院, 福建福州 350108

基金项目:

福州市科技计划 2015H0016

详细信息

通讯作者:
郑玉婴, E-mail:yyzheng@fzu.edu.cn

中图分类号: TB34
计量
- 文章访问数: 115
- HTML全文浏览量: 42
- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2017-01-16
- 修回日期: 2017-04-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-06-10

Preparation of the Mn-Ce-Co-O_x/PPS filter material by a redox method and its activity in the low-temperature selective catalytic reduction of NO_x

College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China

Funds:

the Science and Technology Plan of Fuzhou City 2015H0016

摘要

摘要: 先用十二烷基硫酸钠（SDS）对聚苯硫醚（PPS）滤料进行表面改性，随后通过氧化还原沉淀法制得不同质量比的Mn-Ce-Co-O_x/PPS复合滤料。考察了复合滤料在低温选择性催化还原（SCR）反应过程中的催化活性，并通过XRD、FESEM、TEM和XPS等表征手段对复合滤料的结构及性能进行表征分析。结果表明，Mn-Ce-Co-O_x/PPS复合滤料在120-160 ℃时的脱硝效率达到86%-100%，明显优于超声法制备的Mn-Ce-Co-O_x/PPS-UM复合滤料的低温SCR活性，且1.2Mn-Ce-Co-O_x/PPS复合滤料的活性最优。1.2Mn-Ce-Co-O_x/PPS复合滤料中MnO₂、Ce₂O₃、CeO₂、CoO、Co₃O₄以蜂窝状形式均匀分散在PPS纤维表面，且呈弱结晶性结构；其较高的Ce³⁺/（Ce³⁺+Ce⁴⁺）比值和Co元素浓度是该1.2Mn-Ce-Co-O_x/PPS复合滤料具有优异低温SCR活性的主要原因。此外，与Mn-Ce-Co-O_x/PPS-UM复合滤料相比，1.2Mn-Ce-Co-O_x/PPS复合滤料也具有良好的抗H₂O和抗SO₂性能。
- 十二烷基硫酸钠 /
- 选择性催化还原 /
- PPS滤料 /
- 多元复合催化剂 /
- 脱硝 /
- 抗硫
Abstract: A series of Mn-Ce-Co-O_x/PPS composite filter materials with different mass ratios were obtained by modifying the pristine polyphenylene sulfide (PPS) filter material with sodium dodecyl sulfate (SDS) and then treated by a redox precipitation method. The Mn-Ce-Co-O_x/PPS composite filter materials were characterized by XRD, FESEM, TEM and XPS; their catalytic performance in the low-temperature selective catalytic reduction (SCR) of NO_x was then investigated. The results show that the Mn-Ce-Co-O_x/PPS composite filter materials obtained by the redox method presents higher low-temperature SCR activity than the Mn-Ce-Co-O_x/PPS-UM composite filter material fabricated via the ultrasonic method; over the former material, the NO_x conversion reaches 86%-100% at 120-160℃. Among them, the 1.2Mn-Ce-Co-O_x/PPS composite filter material displays the highest SCR activity, which is probably ascribed to the high Ce³⁺/(Ce³⁺+Ce⁴⁺) ratio and high concentration of Co; moreover, honeycomb-like MnO₂, Ce₂O₃, CeO₂, CoO and Co₃O₄ are uniformly distributed on the PPS filter material in the weak crystalline structure. In comparison with Mn-Ce-Co-O_x/PPS-UM, the 1.2Mn-Ce-Co-O_x/PPS composite filter material also exhibits higher resistance to H₂O and SO₂.
- sodium dodecyl sulfate /
- selective catalytic reduction /
- PPS filter material /
- multivariate composite catalyst /
- denitration /
- sulfur resistance

HTML全文

图 1 Mn-Ce-Co-O_x/PPS复合滤料的制备示意图

Figure 1 Schematic illustration of the procedures for preparing the Mn-Ce-Co-O_x/PPS composite filter material

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图 2 实验装置示意图

Figure 2 Schematic diagram of experiment apparatus for the selective catalytic reduction of NO_x

1: air source; 2: reducing valve; 3: mass flowmeter; 4: commingler; 5: preheater; 6: heater; 7: test sample; 8: flue gas analyzer

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图 3 Mn-Ce-Co-O_x/PPS-UM及Mn-Ce-Co-O_x/PPS复合滤料的SCR活性

Figure 3 SCR activity of Mn-Ce-Co-O_x/PPS-UM and Mn-Ce-Co-O_x/PPS composite filter materials

reaction conditions: [NO]＝[NH₃]＝0.05%, [O₂]＝5%, N₂ as balance gas■: Mn-Ce-Co-O_x/PPS-UM; ●: 0.8Mn-Ce-Co-O_x/PPS; ▲: 1.0Mn-Ce-Co-O_x/PPS; ▼: 1.2Mn-Ce-Co-O_x/PPS; ◆: 1.4Mn-Ce-Co-O_x/PPS

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图 4 原始PPS滤料及不同复合滤料的X射线衍射谱图

Figure 4 XRD patterns of pristine PPS filter material and different composite filter materials

a: pristine PPS filter material; b: 0.8Mn-Ce-Co-O_x/PPS; c: 1.0Mn-Ce-Co-O_x/PPS; d: 1.2Mn-Ce-Co-O_x/PPS; e: 1.4Mn-Ce-Co-O_x/PPS; f: Mn-Ce-Co-O_x/PPS-UM

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图 5 原始PPS滤料、Mn-Ce-Co-O_x/PPS-UM复合滤料和1.2Mn-Ce-Co-O_x/PPS复合滤料的FESEM照片

Figure 5 FESEM images of pristine PPS filter material (a), Mn-Ce-Co-O_x/PPS-UM composite filter material (b) and 1.2Mn-Ce-Co-O_x/PPS composite filter material ((c), (d))

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图 6 原始PPS滤料和1.2Mn-Ce-Co-O_x/PPS复合滤料的TEM照片，1.2Mn-Ce-Co-O_x/PPS复合滤料的HRTEM照片和图(b)中圆形区域的EDX谱图

Figure 6 TEM images of (a) pristine PPS filter material, (b)1.2Mn-Ce-Co-O_x/PPS composite filter material, (c) HRTEM images of 1.2Mn-Ce-Co-O_x/PPS composite filter material and (d) EDX spectrum of the circle area of (b)

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图 7 1.2Mn-Ce-Co-O_x/PPS复合滤料的XPS谱图

Figure 7 XPS spectra of full spectra(a), Mn 2p (b), Ce 3d (c)-a, Co 2p(d), O 1s for 1.2Mn-Ce-Co-O_x/PPS composite filter material (e)-a; Ce 3d (c)-b and O 1s for Mn-Ce-Co-O_x/PPS-UM composite filter material (e)-b

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图 8 H₂O和SO₂对复合滤料SCR活性的影响

Figure 8 Effect of H₂O and SO₂ on the SCR activity of the composite filter materials

reaction conditions: [NO]＝[NH₃]＝0.05%, [O₂]＝5%, N₂ as balance gas■: effect of 5% H₂O on 1.2Mn-Ce-Co-O_x/PPS; ●: effect of 0.01% SO₂ on 1.2Mn-Ce-Co-O_x/PPS; ▲: effect of 5% H₂O on Mn-Ce-Co-O_x/PPS-UM; ▼: effect of 0.01% SO₂ on Mn-Ce-Co-O_x/PPS-UM

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表 1 不同复合滤料中催化剂的负载量

Table 1 Charge of active components in different composite filter materials

表 2 1.2Mn-Ce-Co-O_x/PPS及Mn-Ce-Co-O_x/PPS-UM复合滤料纤维表面铈离子的相对含量

Table 2 Relative content of cerium ion on the fiber surface of 1.2Mn-Ce-Co-O_x/PPS and Mn-Ce-Co-O_x/PPS-UM composite filter materials

表 3 1.2Mn-Ce-Co-O_x/PPS及Mn-Ce-Co-O_x/PPS-UM复合滤料纤维表面氧的相对含量

Table 3 Relative content of oxygen on the fiber surface of 1.2Mn-Ce-Co-O_x/PPS and Mn-Ce-Co-O_x/PPS-UM composite filter materials

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